JP2006053549A - Electrophotographic photosensitive body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photosensitive body which is excellent in wear resistance and electrical characteristics. <P>SOLUTION: The electrophotographic photosensitive body contains polyester resin which is a copolymer of a diphenylether-4,4'-dicarboxylic acid component and a divalent phenol component in a photosensitive layer arranged on a conductive base, wherein the copolymer is represented by general formula (1) and has a viscosity average molecular weight (Mv) of 10,000-300,000. The electrophotographic photosensitive body is excellent in wear resistance and electrical characteristics. In the formula (1), A is a diphenylether-4,4'-dicarboxylic acid residue of a specific structure; and B is a divalent phenol residue of a specific structure. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electrophotographic photosensitive member, and more particularly to an electrophotographic photosensitive member having good wear resistance and the like.

Electrophotographic technology is widely used in the fields of copiers and various printers because of its immediacy and high quality images. As a photoreceptor which is the core of electrophotographic technology, a photoreceptor using an organic photoconductive material having advantages such as non-pollution, easy film formation, and easy manufacture is used.
As a photoconductor using an organic photoconductive material, a so-called dispersion type photoconductor in which a photoconductive fine powder is dispersed in a binder resin and a multi-layer type photoconductor in which a charge generation layer and a charge transfer layer are laminated. Are known. In particular, the laminated type photoconductor can provide a highly sensitive photoconductor by combining a highly efficient charge generating material and a charge transfer material, and can provide a highly safe photoconductor with a wide range of material selection. In addition, the photosensitive layer can be easily formed by coating, has high productivity, and is advantageous in terms of cost. Therefore, the photosensitive layer is the mainstream, and has been developed and put into practical use.

  Since the electrophotographic photosensitive member is repeatedly used in an electrophotographic process, that is, a cycle of charging, exposure, development, transfer, cleaning, static elimination, etc., it is deteriorated by various stresses during that time. Such deterioration includes, for example, strong oxidation ozone generated from a corona charger normally used as a charger, chemical damage given to the photosensitive layer by NOx, and carrier (current) generated by image exposure. There are chemical and electrical degradations such as flow in the photosensitive layer, static electricity removal, or decomposition of the photosensitive layer composition by external light. Further, there is mechanical deterioration such as abrasion of the photosensitive layer due to friction with a cleaning blade, a magnetic brush, etc., contact with the developer, paper, etc., generation of scratches, peeling of the film, and the like. In particular, the damage generated on the surface of the photosensitive layer is likely to appear on the image and directly impairs the image quality, which is a major factor that limits the life of the photoreceptor.

  In the case of a general photoreceptor not provided with a functional layer such as a surface protective layer, the photosensitive layer is subjected to such a load. The photosensitive layer is usually composed of a binder resin and a photoconductive substance, and it is the binder resin that substantially determines the strength, but since the amount of the photoconductive substance doped is considerably large, sufficient mechanical strength is provided. Has not reached. In addition, due to the increasing demand for high-speed printing, materials for a higher-speed electrophotographic process are required. In this case, in addition to high sensitivity and long life, the photosensitive member must have good responsiveness because the time from exposure to development is shortened.

  In addition, each layer constituting these electrophotographic photoreceptors usually has a coating liquid containing a photoconductive substance, a binder resin, etc. on a support, dip coating, spray coating, nozzle coating, bar coating, roll coating, It is formed by coating by blade coating or the like. In these layer forming methods, a known method such as coating is applied as a coating solution obtained by dissolving a substance contained in a layer in a solvent. In many processes, a coating solution is prepared in advance and stored.

  Examples of the binder resin for the photosensitive layer include vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride, and copolymers thereof, thermoplastic resins such as polycarbonate, polyester, polysulfone, phenoxy, epoxy, and silicone resin, and various kinds of heat. A curable resin is used. Among the various binder resins, the polycarbonate resin has a relatively excellent performance, and various polycarbonate resins have been developed and put into practical use (see Patent Documents 1 to 4).

  On the other hand, it has been reported that an electrophotographic photoreceptor using a polyarylate resin marketed under the trade name “U-polymer” as a binder has improved sensitivity as compared with the case of using polycarbonate (Patent Document). 5). In addition, when a polyarylate resin using a dihydric phenol component having a specific structure is used as a binder resin, the stability of the coating solution used in producing an electrophotographic photoreceptor is improved, and further, the electrophotographic photoreceptor It has been reported that the mechanical strength and wear resistance of these are improved (see Patent Document 6 and Patent Document 7).

JP 50-098332 A JP 59-071057 A JP 59-184251 JP 05-021478 A JP-A-56-135844 Japanese Patent Laid-Open No. 03-006567 Japanese Patent Laid-Open No. 10-288845

  By the way, the conventional electrophotographic photosensitive member as described above is worn on the surface due to practical loads such as development with toner, friction with paper, and friction with a cleaning member (blade). The current situation is that the printing performance is limited in practical use due to problems such as scratches.

  In addition, electrophotographic photoreceptors using a conventionally known binder resin often have insufficient electrical properties, although mechanical strength and the like are improved. Furthermore, many coating solutions for forming a photosensitive layer prepared by dissolving such a binder resin in an appropriate solvent have poor solution stability, and as a result, the coating solution becomes cloudy and precipitates. There are problems such as insolubilization of the binder resin.

The present invention has been made to solve such problems.
That is, the object of the present invention is to contain a binder resin that is excellent in wear resistance to a practical load, excellent in electrical characteristics while maintaining high mechanical strength, and further high in the stability of a coating solution for forming a photosensitive layer. The object is to provide an electrophotographic photoreceptor.

  Therefore, as a result of intensive studies, the inventors of the present invention have sufficient mechanical properties by including a polyester resin having a specific chemical structure in the photosensitive layer, and are higher than the solvent used in the coating solution for forming the photosensitive layer. It has been found that an electrophotographic photoreceptor having solubility and excellent coating solution stability and excellent electrical characteristics can be obtained, and the present invention has been completed based on such knowledge.

  That is, according to the present invention, a conductive substrate and a photosensitive layer provided on the conductive substrate are provided, and the photosensitive layer has a repeating structure represented by the following general formulas (1) to (5). An electrophotographic photoreceptor containing at least one polyester resin is provided.

(In general formula (5), {a / (a + b)}> 0.7.)
In the general formula (1) to general formula (5), A is a compound having a structure represented by the following formula (A).

（（Ａ）式中、Ｒａ^１、Ｒａ^２は、各々独立に水素原子または置換基を有することがある一価の置換基であり、ｎ、ｍは、各々独立に０〜４の整数である。）

(In formula (A), Ra ¹ and Ra ² are each independently a monovalent substituent that may have a hydrogen atom or a substituent, and n and m are each independently an integer of 0 to 4. .)

(In formula (1), B is a compound having a structure shown in the following formula (B).)

(In formula (B), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group, a halogen group, or an alkoxy group.)
In formula (2), C is a compound having a structure represented by the following formula (C).

(In the formula (C), R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group, an aryl group, a halogen group, or an alkoxy group.)
In formula (3), D is a compound having a structure represented by the following formula (D).

(In the formula (D), X ¹ represents a single bond or a divalent group.)
In formula (4), E is a compound having a structure represented by the following formula (E).

(In formula (E), R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an aryl group, a halogen group, or an alkoxy group.)
In formula (5), F is a compound having a structure represented by the following formula (F).

(In the formula (F), X ² represents a single bond or a divalent group, and R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group, an aryl group, a halogen group, or an alkoxy group. K and l Each independently represents an integer of 1 to 4.)
In formula (5), G is a compound having a structure represented by the following formula (G).

(In the formula (G), X ³ represents a divalent group.)

  According to the present invention, an electrophotographic photoreceptor excellent in wear resistance and the like can be obtained.

The best mode for carrying out the present invention (hereinafter, an embodiment of the present invention) will be described in detail below. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
The electrophotographic photoreceptor to which the exemplary embodiment is applied includes a photosensitive layer provided on a predetermined conductive substrate, and the photosensitive layer is represented by the general formulas (1) to (5) described above. It contains at least one polyester resin having a structure. As a specific configuration of the photosensitive layer, for example, a laminate in which a charge generation layer mainly composed of a charge generation material and a charge transport layer mainly composed of a charge transport material and a binder resin are stacked on a conductive substrate. Examples include a dispersion type (single layer type) photoreceptor having a photosensitive layer in which a charge generation material is dispersed in a layer containing a charge transport material and a binder resin on a conductive substrate. The above-mentioned polyester resin having a repeating structure represented by the general formula (1) to the general formula (5) is usually used for a layer containing a charge transport material, and preferably used for a charge transport layer of a multilayer photosensitive layer. It is done.

(Conductive substrate)
Examples of the material of the conductive substrate used in the electrophotographic photoreceptor to which the exemplary embodiment is applied include metal materials such as aluminum, aluminum alloy, stainless steel, copper, and nickel; metal, carbon, tin oxide, and the like. Resin material to which conductivity is imparted by adding conductive powder; resin, glass, paper, etc., on which the conductive material such as aluminum, nickel, ITO (indium-tin oxide) is deposited or applied .

Examples of the form of the conductive substrate include a drum shape, a sheet shape, and a belt shape. Further, a conductive material having an appropriate resistance value may be coated on a conductive substrate using a metal material for the purpose of controlling conductivity, surface properties, etc., or covering defects.
When a metal material such as an aluminum alloy is used as the conductive substrate, anodization treatment, chemical conversion film treatment, or the like may be performed in advance. In addition, when performing an anodizing process, it is desirable to perform a sealing process by a well-known method.
The surface of the conductive substrate may be smooth or roughened by a special cutting method or polishing treatment, or by mixing particles having an appropriate particle size with the material constituting the conductive substrate. It may be good.

  As a specific configuration of the photosensitive layer used in the electrophotographic photosensitive member to which the exemplary embodiment is applied, for example, in the case of a laminated type photosensitive member, it contains a charge transport material and a binder resin, and retains an electrostatic charge. And a charge transport layer that transports charges generated by exposure, and a charge generation layer that contains a charge generation material and generates charge pairs by exposure. In addition, there may be a case where a charge blocking layer for blocking charge injection from the conductive substrate, a light diffusion layer for diffusing light such as laser light and preventing interference fringes, etc., as required. is there. In the case of a dispersion type (single layer type) photoreceptor, the photosensitive layer has a charge transport material and a charge generation material dispersed in a binder resin.

(Polyester resin)
Next, the binder resin contained in the photosensitive layer will be described.
In the photosensitive layer used in the electrophotographic photoreceptor to which the exemplary embodiment is applied, at least one polyester resin having a repeating structure represented by the following general formulas (1) to (5) is used as a binder resin. Contains types.

  The viscosity average molecular weight (Mv) of the polyester resin having a repeating structure represented by the general formula (1) to the general formula (5) is not particularly limited, but is usually 10,000 or more, preferably 15,000 or more, Preferably, it is 20,000 or more, provided that it is usually 300,000 or less, preferably 200,000 or less, more preferably 100,000 or less. When the viscosity average molecular weight is excessively small, the mechanical strength of the polyester resin is lowered, which is not practical. On the other hand, if the viscosity average molecular weight is excessively large, it is difficult to apply and form the photosensitive layer to an appropriate film thickness.

  In general formulas (1) to (5), A is a compound having a dicarboxylic acid residue represented by the following formula (A) in the molecule.

Here, in the formula (A), Ra ¹ and Ra ² are each independently a monovalent substituent that may have a hydrogen atom or a substituent, and n and m are each independently an integer of 0 to 4 It is. Examples of the monovalent substituent for Ra ¹ and Ra ² include an alkyl group having 1 to 8 carbon atoms; an aryl group such as a phenyl group and a naphthyl group; a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Halogen group; alkoxy groups such as methoxy group, ethoxy group, butoxy group and the like can be mentioned. Among these, in view of solubility in a coating solution for forming a photosensitive layer as a binder resin for the photosensitive layer, an alkyl group is preferable, more preferably an alkyl group having 1 to 8 carbon atoms, and still more preferably 1 carbon atom. -An alkyl group having 2 carbon atoms. n and m are each independently an integer of 0 to 4, particularly preferably n = m = 0.
Specific examples of the dicarboxylic acid residue represented by the formula (A) include, for example, diphenyl ether-2,2′-dicarboxylic acid residue, diphenyl ether-2,3′-dicarboxylic acid residue, diphenyl ether-2,4 ′. -Dicarboxylic acid residue, diphenyl ether-3,3'-dicarboxylic acid residue, diphenyl ether-3,4'-dicarboxylic acid residue, diphenyl ether-4,4'-dicarboxylic acid residue and the like. Among these, considering the simplicity of production of the dicarboxylic acid component, diphenyl ether-2,2′-dicarboxylic acid residue, diphenyl ether-2,4′-dicarboxylic acid residue, diphenyl ether-4,4′-dicarboxylic acid Residues are preferred, and diphenyl ether-4,4′-dicarboxylic acid residues are particularly preferred.
The compounds exemplified as these diphenyl ether dicarboxylic acid residues (A) can be used in combination with a plurality of compounds as necessary.

  In general formula (1), B is a compound having a dihydric phenol residue represented by the following formula (B) in the molecule.

(B) In the formula, R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, an aryl group, a halogen group, or an alkoxy group. Considering the mechanical properties as the binder resin for the photosensitive layer and the solubility in the solvent when preparing the coating solution for forming the photosensitive layer, the aryl group is preferably a phenyl group, a naphthyl group, etc., and the halogen group is a fluorine atom. , A chlorine atom, a bromine atom, an iodine atom and the like are preferable, and the alkoxy group is preferably a methoxy group, an ethoxy group, a butoxy group or the like. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 2 carbon atoms.

  Specific examples of the dihydric phenol compound to be the dihydric phenol residue represented by the formula (B) include, for example, bis (2-hydroxyphenyl) methane, (2-hydroxyphenyl) (3-hydroxyphenyl) methane, (2-hydroxyphenyl) (4-hydroxyphenyl) methane, bis (3-hydroxyphenyl) methane, (3-hydroxyphenyl) (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, bis (2- Hydroxy-3-methylphenyl) methane, bis (2-hydroxy-3-ethylphenyl) methane, (2-hydroxy-3-methylphenyl) (3-hydroxy-4-methylphenyl) methane, (2-hydroxy-3) -Ethylphenyl) (3-hydroxy-4-ethylphenyl) methane, (2-hydroxy 3-methylphenyl) (4-hydroxy-3-methylphenyl) methane, (2-hydroxy-3-ethylphenyl) (4-hydroxy-3-ethylphenyl) methane, bis (3-hydroxy-4-methylphenyl) Methane, bis (3-hydroxy-4-ethylphenyl) methane, (3-hydroxy-4-methylphenyl) (4-hydroxy-3-methylphenyl) methane, (3-hydroxy-4-ethylphenyl) (4- Hydroxy-3-ethylphenyl) methane, bis (4-hydroxy-3-methylphenyl) methane, bis (4-hydroxy-3-ethylphenyl) methane and the like.

  Among these, bis (4-hydroxyphenyl) methane, (2-hydroxyphenyl) (4-hydroxyphenyl) methane, bis ( 2-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) methane, and bis (4-hydroxy-3-ethylphenyl) methane are particularly preferred. These dihydric phenol components can be used in combination.

  In the general formula (2), C is a compound having a dihydric phenol residue represented by the following formula (C) in the molecule.

(C) In formula, R < ³ >, R < ⁴ > represents a hydrogen atom, an alkyl group, an aryl group, a halogen group, or an alkyl group each independently. Considering the mechanical properties as the binder resin for the photosensitive layer and the solubility in the solvent when preparing the coating solution for forming the photosensitive layer, the aryl group is preferably a phenyl group, a naphthyl group, etc., and the halogen group is a fluorine atom, chlorine An atom, a bromine atom, an iodine atom and the like are preferable, and the alkoxy group is preferably a methoxy group, an ethoxy group, or a butoxy group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 2 carbon atoms.

  Specific examples of the dihydric phenol compound to be the dihydric phenol residue represented by the formula (C) include, for example, 1,1-bis (2-hydroxyphenyl) ethane, 1- (2-hydroxyphenyl) -1 -(3-hydroxyphenyl) ethane, 1- (2-hydroxyphenyl) -1- (4-hydroxyphenyl) ethane, 1,1-bis (3-hydroxyphenyl) ethane, 1- (3-hydroxyphenyl)- 1- (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (2-hydroxy-3-methylphenyl) ethane, 1,1-bis (2-hydroxy-) 3-ethylphenyl) ethane, 1- (2-hydroxy-3-methylphenyl) -1- (3-hydroxy-4-methylphenyl) ethane, 1- (2-hydroxy 3-ethylphenyl) -1- (3-hydroxy-4-ethylphenyl) ethane, 1- (2-hydroxy-3-methylphenyl) -1- (4-hydroxy-3-methylphenyl) ethane, 1- ( 2-hydroxy-3-ethylphenyl) -1- (4-hydroxy-3-ethylphenyl) ethane, 1,1-bis (3-hydroxy-4-methylphenyl) ethane, 1,1-bis (3-hydroxy -4-ethylphenyl) ethane, 1- (3-hydroxy-4-methylphenyl) -1- (4-hydroxy-3-methylphenyl) ethane, 1- (3-hydroxy-4-ethylphenyl) -1- (4-hydroxy-3-ethylphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 1,1-bis (4-hydroxy-3-ethylphenyl) Yl) ethane.

  Among these, 1,1-bis (4-hydroxyphenyl) ethane and 1- (2-hydroxyphenyl) -1- (4-hydroxyphenyl) ethane are considered in consideration of the ease of production of the dihydric phenol compound. 1,1-bis (2-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, and 1,1-bis (4-hydroxy-3-ethylphenyl) ethane are particularly preferable. These dihydric phenol compounds can be used in combination.

  In the general formula (3), D is a compound having a dihydric phenol residue structure represented by the following formula (D) in the molecule.

(D) X ^{1 of the} divalent phenol residue represented by the formula is a single bond or a divalent group. As a suitable divalent group for X ¹ , for example, a sulfur atom, an oxygen atom, a sulfonyl group, a cycloalkylene group, (—CR ¹⁷ R ¹⁸ —) and the like can be mentioned. Here, R ¹⁷ and R ¹⁸ each independently represents a hydrogen atom, an alkyl group, an aryl group, a halogen group or an alkoxy group. Considering the mechanical properties as the binder resin for the photosensitive layer and the solubility in the solvent when preparing the coating solution for forming the photosensitive layer, the aryl group is preferably a phenyl group, a naphthyl group, etc., and the halogen group is a fluorine atom, chlorine An atom, a bromine atom, an iodine atom, etc. are preferable, and as an alkoxy group, a methoxy group, an ethoxy group, a butoxy group, etc. are preferable. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 2 carbon atoms.

In view of the simplicity of production of the dihydric phenol component used for producing the polyester resin, X ¹ may be represented by —O—, —S—, —SO—, —SO ₂ —, —CO—, — CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, a cyclohexylidene group and the like can be mentioned. Among these, preferred are —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, and a cyclohexylidene group, and particularly preferred are —CH ₂ — and a cyclohexylidene group. .

  Specific examples of the dihydric phenol compound to be the dihydric phenol residue represented by the formula (D) include, for example, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, 2, 4,3 ′, 5′-tetramethyl-3,4′-dihydroxybiphenyl, 2,2 ′, 4,4′-tetramethyl-3,3′-dihydroxybiphenyl, bis (4-hydroxy-3,5- Dimethylphenyl) ether, (4-hydroxy-3,5-dimethylphenyl) (3-hydroxy-2,4-dimethylphenyl) ether, bis (3-hydroxy-2,4-dimethylphenyl) ether, bis (4- Hydroxy-3,5-dimethylphenyl) methane, (4-hydroxy-3,5-dimethylphenyl) (3-hydroxy-2,4-dimethylphenyl) methane, bis (3 Hydroxy-2,4-dimethylphenyl) methane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ethane, 1- (4-hydroxy-3,5-dimethylphenyl) -1- (3- Hydroxy-2,4-dimethylphenyl) ethane, 1,1-bis (3-hydroxy-2,4-dimethylphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2 -(4-hydroxy-3,5-dimethylphenyl) -2- (3-hydroxy-2,4-dimethylphenyl) propane, 2,2-bis (3-hydroxy-2,4-dimethylphenyl) propane, , 1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1- (4-hydroxy-3,5-dimethylphenyl) -1- (3-hydroxy- , 4-dimethylphenyl) cyclohexane, 1,1-bis (3-hydroxy-2,4-dimethylphenyl) cyclohexane.

  Among these, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3) are preferable. , 5-dimethylphenyl) methane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1- Bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane and the like can be mentioned.

  Furthermore, considering the simplicity of production of the dihydric phenol compound, bis (4-hydroxy-3,5-dimethylphenyl) methane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane is particularly preferred. These dihydric phenol compounds can be used in combination.

  In the general formula (4), E is a compound having a dihydric phenol residue structure represented by the following formula (E) in the molecule. )

(E) In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a halogen group. Considering the mechanical properties as the binder resin for the photosensitive layer and the solubility in the solvent when preparing the coating solution for forming the photosensitive layer, the aryl group is preferably a phenyl group, a naphthyl group, etc., and the halogen group is a fluorine atom, chlorine An atom, a bromine atom, an iodine atom, etc. are preferable, and as an alkoxy group, a methoxy group, an ethoxy group, a butoxy group, etc. are preferable. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 2 carbon atoms.

  Specific examples of the dihydric phenol compound to be a dihydric phenol residue represented by the formula (E) include, for example, bis (2-hydroxyphenyl) ether, (2-hydroxyphenyl) (3-hydroxyphenyl) ether, (2-hydroxyphenyl) (4-hydroxyphenyl) ether, bis (3-hydroxyphenyl) ether, (3-hydroxyphenyl) (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ether, bis (2- Hydroxy-3-methylphenyl) ether, bis (2-hydroxy-3-ethylphenyl) ether, (2-hydroxy-3-methylphenyl) (3-hydroxy-4-methylphenyl) ether, (2-hydroxy-3) -Ethylphenyl) (3-hydroxy-4-ethylphenyl) ether , (2-hydroxy-3-methylphenyl) (4-hydroxy-3-methylphenyl) ether, (2-hydroxy-3-ethylphenyl) (4-hydroxy-3-ethylphenyl) ether, bis (3-hydroxy -4-methylphenyl) ether, bis (3-hydroxy-4-ethylphenyl) ether, (3-hydroxy-4-methylphenyl) (4-hydroxy-3-methylphenyl) ether, (3-hydroxy-4- Ethylphenyl) (4-hydroxy-3-ethylphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether, bis (4-hydroxy-3-ethylphenyl) ether.

  Among these, bis (4-hydroxyphenyl) ether, (2-hydroxyphenyl) (4-hydroxyphenyl) ether, bis ( 2-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether, bis (4-hydroxy-3-ethylphenyl) ether are particularly preferred. These dihydric phenol compounds can be used in combination.

  In general formula (5), {a / (a + b)}> 0.7, and preferably {a / (a + b)} is 0.8 or more. However, it is 1 or less, preferably 0.9 or less.

The polyester resin having a repeating structure represented by the general formula (5) is a copolymer of a repeating structure represented by-(AF)-and a repeating structure represented by-(GF)-. However, this copolymer may be a random copolymer of the two types of repeating units described above or a block copolymer. In the case of a block copolymer, a multi-block copolymer may be used. Among these, a random copolymer is preferable in terms of ease of production.
In general formula (5), F is a compound having a dihydric phenol residue structure represented by the following formula (F) in the molecule.

(F) X ² of the dihydric phenol compound to be the dihydric phenol residue represented by the formula is a single bond or a divalent group, and examples of suitable divalent groups include a sulfur atom, an oxygen atom, and a sulfonyl group. , A cycloalkylene group, (—CR ¹⁹ R ²⁰ —) and the like. Here, R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, an alkyl group, an aryl group, a halogen group, or an alkoxy group. Considering the mechanical properties as the binder resin for the photosensitive layer and the solubility in the solvent when preparing the coating solution for forming the photosensitive layer, the aryl group is preferably a phenyl group, a naphthyl group, etc., and the halogen group is a fluorine atom, chlorine An atom, a bromine atom, an iodine atom, etc. are preferable, and as an alkoxy group, a methoxy group, an ethoxy group, a butoxy group, etc. are preferable. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 2 carbon atoms.

Furthermore, considering the simplicity of production of a dihydric phenol compound that becomes a dihydric phenol residue used in producing a polyester resin, X ^{2 can} be represented by —O—, —S—, —SO—, —SO _{2. -, - CO -, - CH} 2 -, - CH (CH 3) -, - C (CH 3) 2 -, cyclohexylidene group and the like. Among these, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, and a cyclohexylidene group are particularly preferable.

(F) In formula, R < ⁷ >, R < ⁸ > represents a hydrogen atom, an alkyl group, an aryl group, a halogen group, or an alkyl group each independently. Considering the mechanical properties as the binder resin for the photosensitive layer and the solubility in the solvent when preparing the coating solution for forming the photosensitive layer, the aryl group is preferably a phenyl group, a naphthyl group, etc., and the halogen group is a fluorine atom, chlorine An atom, a bromine atom, an iodine atom, etc. are preferable, and as an alkoxy group, a methoxy group, an ethoxy group, a butoxy group, etc. are preferable. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 2 carbon atoms. K and l each independently represent an integer of 1 to 4.

  Particularly preferred as specific examples of the formula (F) are, for example, bis (4-hydroxyphenyl) methane, (2-hydroxyphenyl) (4-hydroxyphenyl) methane, bis (2-hydroxyphenyl) methane, 1,1 -Bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy Phenyl) ether, bis (4-hydroxy-3-methylphenyl) methane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, bis (4-hydroxy- -Methylphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ethane, 2,2-bis (4-hydroxy-) 3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane and the like. These dihydric phenol compounds can be used in combination.

  In general formula (5), G is a compound having a dicarboxylic acid residue structure represented by the following formula (G) in the molecule.

In formula (G), X ³ is a divalent group. Examples of suitable divalent groups for X ³ include divalent groups of saturated aliphatic hydrocarbons such as methylene group and ethylene group; p-phenylene group, 1,4-naphthylene group, 3-methyl-p-phenylene group. An arylene group which may have a substituent such as.

  Specific examples of the dicarboxylic acid residue represented by the formula (G) include, for example, dicarboxylic acid residues of saturated aliphatic hydrocarbons such as adipic acid residues, suberic acid residues, and sebacic acid residues; Group, isophthalic acid residue, terephthalic acid residue, aromatic hydrocarbon dicarboxylic acid residue such as toluene-2,5-dicarboxylic acid residue; p-xylene-2,5-dicarboxylic acid residue, pyridine- 2,3-dicarboxylic acid residue, pyridine-2,4-dicarboxylic acid residue, pyridine-2,5-dicarboxylic acid residue, pyridine-2,6-dicarboxylic acid residue, pyridine-3,4-dicarboxylic acid Residues, heterocyclic dicarboxylic acid residues such as pyridine-3,5-dicarboxylic acid residues; naphthalene-1,4-dicarboxylic acid residues, naphthalene-2,3-dicarboxylic acid residues, naphthalene-2,6 -Dicarboxylic acid residue Condensed polycyclic dicarboxylic acid residue and the like; 2,2'-dicarboxylic acid residue include dicarboxylic acid residues hydrocarbon ring group of biphenyl-4,4'-dicarboxylic acid residue. Among these, Preferably, adipic acid residue, sebacic acid residue, phthalic acid residue, isophthalic acid residue, terephthalic acid residue, naphthalene-1,4-dicarboxylic acid residue, naphthalene-2,6- Examples thereof include a dicarboxylic acid residue, a biphenyl-2,2′-dicarboxylic acid residue, and a biphenyl-4,4′-dicarboxylic acid residue. More preferred are aromatic hydrocarbon dicarboxylic acid residues, and particularly preferred are isophthalic acid residues and terephthalic acid residues. These dicarboxylic acid residues can be used in combination.

  The photosensitive layer in the electrophotographic photoreceptor to which the exemplary embodiment is applied is a mixture of the polyester resin having a repeating structure represented by the general formula (1) to the general formula (5) and another resin. It can also be used. Other resins mixed here include, for example, vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride or copolymers thereof; polycarbonate resin, polyester resin, polyester polycarbonate resin, polysulfone resin, phenoxy resin, epoxy Examples thereof include thermoplastic resins such as resins and silicone resins, and various thermosetting resins. Of these resins, polycarbonate resin is preferable. Moreover, the mixing ratio of the resin to be used in combination is not particularly limited, but it is usually preferable to use the resin in a range not exceeding the ratio of the polyester resin having a repeating structure represented by the general formula (1) to the general formula (5). .

(Production method of polyester resin)
Next, the manufacturing method of the polyester resin which has a repeating structure represented by General formula (1)-General formula (5) is demonstrated.
The method for producing a polyester resin having a repeating structure represented by the general formula (1) to the general formula (5) is not particularly limited, and examples thereof include known polymerization methods such as an interfacial polymerization method, a melt polymerization method, and a solution polymerization method. The method can be used.

  In the case of production by the interfacial polymerization method, for example, a solution in which a dihydric phenol component is dissolved in an alkaline aqueous solution and a halogenated hydrocarbon solution in which an aromatic dicarboxylic acid chloride component is dissolved are mixed. At this time, a quaternary ammonium salt or a quaternary phosphonium salt may be present as a catalyst. The polymerization temperature is preferably in the range of 0 ° C. to 40 ° C., and the polymerization time is preferably in the range of 2 hours to 20 hours from the viewpoint of productivity. After completion of the polymerization, the water phase and the organic phase are separated, and the polymer dissolved in the organic phase is washed and recovered by a known method, whereby the intended resin can be obtained.

  Examples of the alkali component used in the interfacial polymerization method include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The amount of alkali used is preferably in the range of 1.01 to 3 equivalents of the phenolic hydroxyl group contained in the reaction system. Examples of the halogenated hydrocarbon include dichloromethane, chloroform, 1,2-dichloroethane, trichloroethane, tetrachloroethane, dichlorobenzene, and the like. Examples of quaternary ammonium salts or quaternary phosphonium salts used as catalysts include, for example, salts of tertiary alkylamines such as tributylamine and trioctylamine such as hydrochloric acid, bromic acid and iodic acid; benzyltriethylammonium chloride, benzyltrimethylammonium Examples include chloride, benzyltributylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, tetrabutylphosphonium bromide, triethyloctadecylphosphonium bromide, N-laurylpyridinium chloride, laurylpicolinium chloride It is done.

  In the interfacial polymerization method, a molecular weight regulator can be used. Examples of the molecular weight regulator include phenol, o, m, p-cresol, o, m, p-ethylphenol, o, m, p-propylphenol, o, m, p- (tert-butyl) phenol, and pentyl. Alkylphenols such as phenol, hexylphenol, octylphenol, nonylphenol, 2,6-dimethylphenol derivatives and 2-methylphenol derivatives; monofunctional phenols such as o, m, p-phenylphenol; acetic acid chloride, butyric acid chloride, octyl Examples thereof include monofunctional acid halides such as acid chloride, benzoyl chloride, benzenesulfonyl chloride, benzenesulfinyl chloride, sulfinyl chloride, benzenephosphonyl chloride, and substituted products thereof. Among these molecular weight regulators, o, m, p- (tert-butyl) phenol, 2,6-dimethylphenol derivatives, 2-methylphenol derivatives are preferred because of their high molecular weight controllability and solution stability. It is. Particularly preferred are p- (tert-butyl) phenol, 2,3,6-trimethylphenol, and 2,3,5-trimethylphenol.

Next, other components contained in the photosensitive layer of the electrophotographic photoreceptor to which the exemplary embodiment is applied will be described.
(Charge generation layer)
When the electrophotographic photosensitive member to which the exemplary embodiment is applied is a laminated type photosensitive member, the charge generating layer constituting the photosensitive layer contains a charge generating substance. Examples of charge generation materials include selenium and its alloys, cadmium sulfide, and other inorganic photoconductive materials; phthalocyanine pigments, azo pigments, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, anthanthrone pigments, benzimidazole pigments And various photoconductive materials such as organic pigments. Among these, organic pigments, phthalocyanine pigments, and azo pigments are particularly preferable. The fine particles of these charge generating materials are, for example, polyester resin, polyvinyl acetate, polyacrylate ester, polymethacrylate ester, polyester, polycarbonate, polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral, phenoxy resin, epoxy resin, urethane resin. , Cellulose ester, cellulose ether, and other binder resins. Although the usage-amount of a charge generation substance is not specifically limited, Usually, it is used in 30 weight part-500 weight part with respect to 100 weight part of binder resin. The thickness of the charge generation layer is usually 0.1 μm to 1 μm, preferably 0.15 μm to 0.6 μm.

  When a phthalocyanine compound is used as a charge generation material, specifically, metal-free phthalocyanine, copper, indium, gallium, tin, titanium, zinc, vanadium, silicon, germanium, or other metals or their oxides, halides, etc. coordination Phthalocyanines are used. Examples of the ligand to a trivalent or higher metal atom include an oxygen atom, a chlorine atom, a hydroxyl group, an alkoxy group, and the like. In particular, highly sensitive X-type, τ-type metal-free phthalocyanine, A-type, B-type, D-type titanyl phthalocyanine, vanadyl phthalocyanine, chloroindium phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, and the like are suitable. Of the crystal forms of titanyl phthalocyanine mentioned here, A type and B type are described in W.W. It has been shown by Heller et al. As phase I and phase II, respectively (Zeit. Kristallogr. 159 (1982) 173), and type A is known as a stable type. The D type is a crystal type showing a clear peak at a diffraction angle 2θ ± 0.2 ° of 27.3 ° in powder X-ray diffraction using CuKα rays. As the phthalocyanine compound, only a single compound may be used, or several mixed states may be used. As the mixed state that can be placed in the phthalocyanine compound or crystal state here, the respective constituent elements may be mixed and used later, or the mixed state in the production / treatment process of the phthalocyanine compound such as synthesis, pigmentation, crystallization, etc. It may be generated. As such treatment, acid paste treatment, grinding treatment, solvent treatment and the like are known.

(Charge transport layer)
When the electrophotographic photosensitive member to which this exemplary embodiment is applied is a laminated type photosensitive member, the charge transporting layer constituting the photosensitive layer contains a charge transporting substance. Examples of charge transport materials include aromatic nitro compounds such as 2,4,7-trinitrofluorenone; cyano compounds such as tetracyanoquinodimethane; electron-withdrawing materials such as quinones such as diphenoquinone; carbazole derivatives, indoles Heterocyclic compounds such as derivatives, imidazole derivatives, oxazole derivatives, pyrazole derivatives, oxadiazole derivatives, pyrazoline derivatives, thiadiazole derivatives; aniline derivatives, hydrazone compounds, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, enamine compounds or these compounds Or an electron donating substance such as a polymer having a group consisting of these compounds in the main chain or side chain. Among these, carbazole derivatives, hydrazone derivatives, aromatic amine derivatives, stilbene derivatives, butadiene derivatives and those in which a plurality of these derivatives are bonded are preferable, and those in which a plurality of aromatic amine derivatives, stilbene derivatives, and butadiene derivatives are bonded. Is preferred.

  Among charge transport materials, a compound having a structure represented by the following general formula (6) is preferably used.

In General Formula (6), Ar ^{1 to} Ar ⁶ each independently represent an arylene group that may have a substituent or a divalent heterocyclic group that may have a substituent. m ¹ and m ² each independently represents 0 or 1. Ar ⁵ in the case of m ¹ = 0 and Ar ^{6 in} the case of m ² = 0 each have an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. It may be a monovalent heterocyclic group. Ar ⁵ in the case of m ¹ = 1 and Ar ^{6 in} the case of m ² = 1 each have an alkylene group that may have a substituent, an arylene group that may have a substituent, or a substituent. Represents a divalent heterocyclic group which may be substituted. Q represents a direct bond or a divalent residue. R ^{9 to} R ¹⁶ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent. . n ¹ ~n ⁴ represents each independently integers from 0-4. Ar ^{1 to} Ar ⁶ may be bonded to each other to form a cyclic structure.

Furthermore, in general formula (6), R ^{9 to} R ¹⁶ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. It represents an aralkyl group which may have a heterocyclic group which may have a substituent.

In general formula (6), examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a cyclopentyl group, and a cyclohexyl group. Of these, an alkyl group having 1 to 6 carbon atoms is preferred. When the alkyl group has an aryl substituent, examples thereof include a benzyl group and a phenethyl group, and an aralkyl group having 7 to 12 carbon atoms is preferable.
Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a pyrenyl group, and an aryl group having 6 to 12 carbon atoms is preferable.
The heterocyclic group is preferably an aromatic heterocyclic ring, and examples thereof include a furyl group, a thienyl group, and a pyridyl group, and a monocyclic aromatic heterocyclic ring is more preferable. In R ^{7 to} R ¹⁴ , the most preferred are a methyl group and a phenyl group.

In General Formula (6), Ar ^{1 to} Ar ⁶ each independently represent an arylene group that may have a substituent or a divalent heterocyclic group that may have a substituent. m ¹ and m ² each independently represents 0 or 1. Ar ⁵ in the case of m ¹ = 0 and Ar ^{6 in} the case of m ² = 0 each have an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. Represents a monovalent heterocyclic group which may be substituted, Ar ⁵ in the case of m ¹ = 1, and Ar ⁶ in the case of m ² = 1 each have an alkylene group and a substituent which may have a substituent. An arylene group that may be substituted, or a divalent heterocyclic group that may have a substituent. Specifically, examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a pyrenyl group, and an aryl group having 6 to 14 carbon atoms is preferable; the arylene group includes a phenylene group and a naphthylene group. A phenylene group is preferable.

In the general formula (6), the monovalent heterocyclic group is preferably an aromatic heterocyclic ring, and examples thereof include a furyl group, a thienyl group, a pyridyl group, and the like. preferable. As the divalent heterocyclic group, an aromatic heterocyclic ring is preferable, and examples thereof include a pyridylene group and a thienylene group, and a monocyclic aromatic heterocyclic ring is more preferable. Of these, the most preferred are Ar ¹ and Ar ² are phenylene groups, and Ar ³ is a phenyl group.

In general formula (6), among the groups represented by R ^{9 to} R ¹⁶ and Ar ^{1 to} Ar ⁶ , the alkyl group, aryl group, aralkyl group, and heterocyclic group may further have a substituent. . Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, and tert-butyl. Group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group and other alkyl groups; methoxy group, ethoxy group, propyloxy group and other alkoxy groups; methylthio group, ethylthio group and other alkylthio groups; vinyl group, allyl group and other alkenyl groups Groups; aralkyl groups such as benzyl, naphthylmethyl, and phenethyl groups; aryloxy groups such as phenoxy and triloxy groups; arylalkoxy groups such as benzyloxy and phenethyloxy groups; aryl groups such as phenyl and naphthyl groups; Aryl vinyl groups such as styryl groups and naphthyl vinyl groups; Acyl groups such as til group and benzoyl group; Dialkylamino groups such as dimethylamino group and diethylamino group; Diarylamino groups such as diphenylamino group and dinaphthylamino group; Diaralkylamino groups such as dibenzylamino group and diphenethylamino group A diheterocyclic amino group such as a group, a dipyridylamino group or a dithienylamino group; a substituted amino group such as a diallylamino group or a disubstituted amino group obtained by combining substituents of the amino group described above; and a cyano group, a nitro group, A hydroxyl group etc. are mentioned. These substituents may be bonded to each other to form a cyclic hydrocarbon group or a heterocyclic group via a single bond, a methylene group, an ethylene group, a carbonyl group, a vinylidene group, an ethylenylene group or the like.

  Among these, preferred substituents include a halogen atom, a cyano group, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and 6 to 12 carbon atoms. An arylthio group having 6 to 12 carbon atoms, and a dialkylamino group having 2 to 8 carbon atoms, more preferably a halogen atom, an alkyl group having 1 to 6 carbon atoms, and a phenyl group, and a methyl group and a phenyl group. Is particularly preferred.

In General Formula (6), n ^{1 to} n ⁴ each independently represents an integer of 0 to 4, preferably 0 to 2, and particularly preferably 1. m ¹ and m ² represent 0 or 1, and 0 is preferable.

  In general formula (6), Q represents a direct bond or a divalent residue, and a preferable divalent residue is a group 16 atom, an alkylene which may have a substituent, or a substituent. An arylene group which may be substituted, a cycloalkylidene group which may have a substituent, or a group in which these are bonded to each other, for example, [—O—Z—O—], [—Z—O—Z—], [—S— Z—S—], [—Z—Z—] and the like (provided that O is an oxygen atom, S is a sulfur atom, and Z may have an arylene group or substituent which may have a substituent). Represents a good alkylene group).

  As an alkylene group which comprises Q, a C1-C6 thing is preferable and a methylene group and an ethylene group are still more preferable especially. Moreover, as a cycloalkylidene group, a C5-C8 thing is preferable and a cyclopentylidene group and a cyclohexylidene group are still more preferable especially. As the arylene group, those having 6 to 14 carbon atoms are preferable, and among them, a phenylene group and a naphthylene group are more preferable.

  These alkylene groups, arylene groups, and cycloalkylidene groups may have a substituent. Preferred substituents include a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, and a carbon number. Examples thereof include an alkenyl group having 1 to 6 carbon atoms and an aryl group having 6 to 14 carbon atoms.

  Specific examples of the charge transport material contained in the charge transport layer constituting the photosensitive layer of the electrophotographic photoreceptor to which the exemplary embodiment is applied include, for example, arylamines described in JP-A-9-244278 Compounds, arylamine compounds described in JP-A-2002-275133, and the like. These charge transport materials may be used alone or in combination. The charge transport layer is formed in such a form that these charge transport materials are bound to the binder resin. The charge transport layer may be composed of a single layer, or may be a stack of a plurality of layers having different constituent components or composition ratios.

  The ratio of the binder resin made of the polyester resin having a repeating structure represented by the general formula (1) to the general formula (5) and the charge transport material is usually 30 parts by weight of the charge transport material with respect to 100 parts by weight of the binder resin. It is used in the range of ~ 200 parts by weight, preferably 40 parts by weight to 150 parts by weight. The film thickness of the charge transport layer is usually 5 μm to 50 μm, preferably 10 μm to 45 μm.

  It should be noted that the charge transport layer has well-known plasticizers, antioxidants, ultraviolet absorbers, and electron withdrawing properties in order to improve film forming properties, flexibility, coating properties, stain resistance, gas resistance, light resistance, etc. You may contain additives, such as a compound, dye, a pigment, and a leveling agent. Examples of the antioxidant include hindered phenol compounds and hindered amine compounds. Examples of dyes and pigments include various pigment compounds and azo compounds.

(Dispersion (single layer) photosensitive layer)
In the case of a dispersion type photosensitive layer, the above-described charge generating material is dispersed in a charge transport medium comprising the above-described binder resin and a charge transport material. The particle size of the charge generation material needs to be sufficiently small, and is preferably 1 μm or less, more preferably 0.5 μm or less. If the amount of the charge generating material dispersed in the photosensitive layer is excessively small, sufficient sensitivity cannot be obtained. If it is excessively large, there are problems such as a decrease in chargeability and a decrease in sensitivity. The amount of the charge generating material used is preferably in the range of 0.5 wt% to 50 wt%, more preferably 1 wt% to 20 wt%.

  The film thickness of the dispersion type photosensitive layer is usually 5 μm to 50 μm, more preferably 10 μm to 45 μm. Also in this case, known plasticizers for improving film formability, flexibility, mechanical strength, additives for suppressing residual potential, dispersion aids for improving dispersion stability, coatability Leveling agents and surfactants such as silicone oil, fluorine oil and other additives may be added to improve the viscosity. On the dispersion type photosensitive layer, a protective layer may be provided for the purpose of preventing the wear of the dispersion type photosensitive layer or preventing or reducing the degradation of the dispersion type photosensitive layer due to discharge products generated from a charger or the like. . Further, for the purpose of reducing frictional resistance and wear on the surface of the electrophotographic photosensitive member, the surface layer may contain a fluorine resin, a silicone resin, or the like. Moreover, the particle | grains which consist of these resin, and the particle | grains of an inorganic compound may be included.

(Method for preparing electrophotographic photoreceptor)
The method for preparing the electrophotographic photosensitive member to which the exemplary embodiment is applied is not particularly limited, but is usually a polyester having a repeating structure represented by general formula (1) to general formula (5) on a conductive substrate. The photosensitive layer forming coating solution containing a resin is formed by coating by a known method such as a dip coating method, a spray coating method, a nozzle coating method, a bar coating method, a roll coating method, or a blade coating method. Among these, the dip coating method is preferable because of its high productivity.

(Underlayer)
In the electrophotographic photoreceptor to which this exemplary embodiment is applied, an undercoat layer may be provided between the conductive substrate and the photosensitive layer in order to improve adhesion and blocking properties. As the undercoat layer, for example, a resin, a resin in which particles such as a metal oxide are dispersed, or the like is used. Examples of the metal oxide particles used for the undercoat layer include, for example, metal oxide particles containing one metal element such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, iron oxide, and calcium titanate. And metal oxide particles containing a plurality of metal elements such as strontium titanate and barium titanate. As these metal oxide particles, only one kind of particles may be used, or a plurality of kinds of particles may be mixed and used.

  Among these, titanium oxide and aluminum oxide are preferable, and titanium oxide is particularly preferable. The surface of the titanium oxide particles may be treated with an inorganic substance such as tin oxide, aluminum oxide, antimony oxide, zirconium oxide, or silicon oxide, or an organic substance such as stearic acid, polyol, or silicone. As the crystal form of the titanium oxide particles, any of rutile, anatase, brookite, and amorphous can be used. A thing of a several crystalline state may be contained. In addition, various particle sizes of the metal oxide particles can be used. Among them, from the viewpoint of characteristics and liquid stability, the average temporary particle size is preferably 10 nm or more and 100 nm or less, and particularly preferably 10 nm or more. 50 nm or less.

  The undercoat layer is preferably formed in a form in which metal oxide particles are dispersed in a binder resin. As binder resin used for the undercoat layer, phenoxy, epoxy, polyvinyl pyrrolidone, polyvinyl alcohol, casein, polyacrylic acid, celluloses, gelatin, starch, polyurethane, polyimide, polyamide, etc. are used alone or in a cured form together with a curing agent. Among them, alcohol-soluble copolymerized polyamides, modified polyamides and the like are preferable because they exhibit good dispersibility and coating properties. The compounding composition ratio of the metal oxide particles with respect to the binder resin is not particularly limited, but it is usually preferable in the range of 10% by weight to 500% by weight in terms of stability of the dispersion and coatability. The thickness of the undercoat layer is not particularly limited, but is preferably 0.1 μm to 20 μm in view of the photoreceptor characteristics and applicability. Moreover, you may add a well-known antioxidant etc. to an undercoat layer.

Next, an example of an image forming apparatus using the electrophotographic photoreceptor to which the exemplary embodiment is applied will be described.
FIG. 1 is a diagram illustrating an image forming apparatus. The image forming apparatus 10 shown in FIG. 1 contains a photosensitive resin containing at least one polyester resin having a repeating structure represented by the general formulas (1) to (5) described above on a predetermined conductive substrate. An electrophotographic photosensitive member 1 provided with a layer; a charging device 2 comprising a charging roller for charging the electrophotographic photosensitive member 1; an exposure device 3 for forming an electrostatic latent image on the photosensitive surface of the electrophotographic photosensitive member 1; Formed on the electrophotographic photosensitive member 1 by applying a predetermined voltage value (transfer voltage) having a polarity opposite to the charging potential of the toner (T) to the developing device 4 for supplying the toner (T) to the surface of the photographic photosensitive member 1 The transfer device 5 for transferring the toner image to the recording paper (P), the cleaning device 6 for scraping and collecting the residual toner adhering to the electrophotographic photosensitive member 1, and the toner image transferred to the recording paper (P) are fixed. And a fixing device 7.

The electrophotographic photosensitive member 1 has a drum shape in which a photosensitive layer containing at least one kind of the above-described polyester resin is provided on the surface of a cylindrical conductive substrate.
The charging device 2 has a roller-type charging roller. As the charging device 2, for example, a corona charging device such as corotron or scorotron, a contact charging device such as a charging brush, and the like are often used. In many cases, the electrophotographic photoreceptor 1 and the charging device 2 are designed to be removable from the main body of the image forming apparatus 10 as a cartridge having both of them (hereinafter also referred to as a photoreceptor cartridge). ing. For example, when the electrophotographic photoreceptor 1 or the charging device 2 is deteriorated, the photoreceptor cartridge can be detached from the main body of the image forming apparatus 10 and another new photoreceptor cartridge can be mounted on the main body of the image forming apparatus. (Not shown).

  The type of the exposure apparatus 3 is not particularly limited as long as it can form an electrostatic latent image on the photosensitive surface of the electrophotographic photoreceptor 1. Specific examples include halogen lamps, fluorescent lamps, lasers such as semiconductor lasers and He—Ne lasers, LEDs, and the like. The exposure can also be performed by a photoreceptor internal exposure method. The light used for the exposure is not particularly limited, and examples thereof include monochromatic light having a wavelength of 780 nm, monochromatic light having a wavelength slightly shorter than 600 nm to 700 nm, and monochromatic light having a short wavelength of 380 nm to 500 nm.

  The developing device 4 includes a developing tank 41 in which toner (T) is stored. Further, the developing tank 41 carries an agitator 42 for stirring the toner (T) and the stored toner (T). Then, a supply roller 43 supplied to a developing roller 44, which will be described later, and the electrophotographic photosensitive member 1 and the supply roller 43 are brought into contact with each other, and carry toner (T) supplied by the supply roller 43 to carry the electrophotographic photosensitive member 1. The developing roller 44 is brought into contact with the surface, and the regulating member 45 is in contact with the developing roller 44. If necessary, a replenishing device (not shown) for replenishing toner (T) from a container such as a bottle or cartridge to the developing tank 41 may be attached. The type of the developing device 4 is not particularly limited, and any device such as a dry development method such as cascade development, one-component conductive toner development, or two-component magnetic brush development, or a wet development method can be used.

  The agitator 42 is rotated by a rotation driving mechanism, and agitates the toner (T) and conveys the toner (T) to the supply roller 43 side. A plurality of agitators 42 may be provided with different blade shapes and sizes. The supply roller 43 is formed from, for example, a conductive sponge. The developing roller 44 is made of a metal roll such as iron, stainless steel, aluminum, or nickel, or a resin roll obtained by coating a metal roll with a silicone resin, a urethane resin, a fluororesin, or the like. The surface of the developing roller 44 may be smoothed or roughened as necessary. The regulating member 45 is formed of a resin blade such as a silicone resin or a urethane resin, a metal blade such as stainless steel, aluminum, copper, brass, phosphor bronze, or a blade obtained by coating a metal blade with a resin. The regulating member 45 is in contact with the developing roller 44 and pressed against the developing roller 44 side with a predetermined force by a spring or the like (a general blade linear pressure is 5 to 500 g / cm). If necessary, the regulating member 45 may be provided with a function of charging the toner (T) by frictional charging with the toner (T). The supply roller 43 and the developing roller 44 are rotated by a rotation drive mechanism (not shown).

  The type of the toner (T) is not particularly limited, but normally, besides a powdery toner, a polymerized toner using a suspension polymerization method, an emulsion polymerization method, or the like can be used. In particular, when a polymerized toner is used, a toner having a small particle diameter of about 4 to 8 μm is preferable, and the toner (T) particles have a variety of shapes ranging from a nearly spherical shape to those outside a potato-like spherical shape. Can be used for The polymerized toner is excellent in charging uniformity and transferability and is suitably used for high image quality. In many cases, the toner (T) is stored in the toner cartridge and designed to be removable from the main body of the image forming apparatus 10, and when the toner (T) in the used toner cartridge is used up, The toner cartridge can be removed from the main body of the image forming apparatus 10 and another new toner cartridge can be mounted. Further, a cartridge provided with the electrophotographic photoreceptor 1, the charging device 2, and the toner (T) can be used.

  Although not shown, the transfer device 5 includes a transfer charger, a transfer roller, a transfer belt, and the like disposed so as to face the electrophotographic photoreceptor 1. The type of the transfer device 5 is not particularly limited. For example, an apparatus using an arbitrary method such as an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, or an adhesive transfer method is used. Can do.

  The cleaning device 6 is not particularly limited, and any cleaning device such as a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, or the like can be used.

  The fixing device 7 includes an upper fixing member 71 made of a fixing roller, a lower fixing member 72 made of a fixing roller that contacts the upper fixing member 71, and a heating device 73 provided inside the upper fixing member 71. ing. The heating device 73 may be provided inside the lower fixing member 72. The upper fixing member 71 or the lower fixing member 72 is a known heat fixing member such as a fixing roll in which a metal base tube such as stainless steel or aluminum is coated with silicone rubber, a fixing roll in which Teflon (registered trademark) resin is coated, or a fixing sheet. Can be used. Furthermore, the upper fixing member 71 or the lower fixing member 72 may be configured to supply a release agent such as silicone oil in order to improve the releasability, or may be configured to forcibly apply pressure to each other by a spring or the like. . The type of the fixing device 7 is not particularly limited, and for example, a fixing device of an arbitrary system such as heat roller fixing, flash fixing, oven fixing, pressure fixing, or the like can be provided.

Next, the operation of the image forming apparatus 10 will be described.
The surface (photosensitive surface) of the electrophotographic photosensitive member 1 is charged to a predetermined potential (for example, −600 V) by the charging device 2. At this time, charging may be performed by a DC voltage, or charging may be performed by superimposing an AC voltage on the DC voltage. Subsequently, the photosensitive surface of the charged electrophotographic photosensitive member 1 is exposed by the exposure device 3 according to the image to be recorded, and an electrostatic latent image is formed on the photosensitive surface. Next, development of the electrostatic latent image formed on the photosensitive surface of the electrophotographic photosensitive member 1 is performed by the developing device 4. That is, the developing device 4 thins the toner (T) supplied by the supply roller 43 with a regulating member 45 such as a developing blade and also has a predetermined polarity (here, the same as the charging potential of the electrophotographic photosensitive member 1). Polarity and negative polarity) are triboelectrically charged, conveyed while being carried on the developing roller 44, and brought into contact with the surface of the electrophotographic photosensitive member 1.

  When the charged toner (T) carried on the developing roller 44 comes into contact with the surface of the electrophotographic photoreceptor 1, a toner image corresponding to the electrostatic latent image is formed on the photosensitive surface of the electrophotographic photoreceptor 1. Subsequently, the toner image is transferred to the recording paper (P) by the transfer device 5. Thereafter, the toner (T) remaining on the photosensitive surface of the electrophotographic photosensitive member 1 without being transferred is removed by the cleaning device 6. When the toner (T) transferred onto the recording paper (P) passes between the upper fixing member 71 and the lower fixing member 72 heated to a predetermined temperature, the toner (T) is heated to a molten state. Then, after cooling, the toner (T) is fixed on the recording paper (P), and a final image is obtained.

  In addition to the above-described configuration, the image forming apparatus 10 may have a configuration capable of performing a static elimination process, for example. The neutralization process is a process of neutralizing the electrophotographic photosensitive member 1 by exposing the electrophotographic photosensitive member 1, and a fluorescent lamp, an LED, or the like is used as the neutralizing device. In addition, the light used in the static elimination process is often light having an exposure energy that is at least three times that of the exposure light.

  The image forming apparatus 10 may be further modified. For example, the image forming apparatus 10 may be configured to perform a pre-exposure process, an auxiliary charging process, or the like, or may be configured to perform offset printing. A full color tandem system configuration using the toner (T) may be used.

  Hereinafter, the present embodiment will be described more specifically based on examples. Note that this embodiment is not limited to the examples. In the examples and comparative examples, parts and% are based on weight unless otherwise specified.

(Viscosity average molecular weight (Mv))
Using a Ubbelohde capillary viscometer (dichloromethane flow time t ₀ : 136.16 seconds), the flow time (t) of a polyester resin dichloromethane solution (concentration: 6.00 g / L) was measured at 20.0 ° C. Based on the following formula, the viscosity average molecular weight (Mv) of the polyester resin was calculated. The results are shown in Table 1, Table 2, and Tables 4 to 7.
η _sp = (t / t ₀ ) −1
a = 0.438 × η _sp +1
b = 100 × (η _sp / C)
C = 6.00 [g / L]
η = b / a
Mv = 3207 × η ^1.205

(Electrical characteristics test)
Photosensitive sheet prepared in advance using an electrophotographic characteristic evaluation apparatus (basic and applied electrophotographic technology, edited by Electrophotographic Society, Corona, pages 404-405) compliant with the Electrophotographic Society measurement standard (To be described later) is affixed to an aluminum drum to form a cylinder, and after the aluminum drum and the aluminum base of the photosensitive sheet are electrically connected, the drum is rotated at a constant rotational speed, charging, exposure, potential measurement, An electrical property evaluation test was carried out by a charge removal cycle. The initial surface potential was −700 V, the exposure light was 780 nm, the neutralization light was 660 nm, and the surface potential (VL) was measured when the exposure light was irradiated at 2.4 μJ / cm ² . In the VL measurement, the time required from the exposure to the potential measurement was 139 ms. The measurement environment was a temperature of 25 ° C. and a relative humidity of 50% (NN environment), and a temperature of 5 ° C. and a relative humidity of 10% (LL environment). The smaller the absolute value of the VL value, the better the response (unit: -V). The results are shown in Tables 1 and 7.

(Abrasion test)
A photoconductor sheet (described later) prepared in advance was cut into a circle having a diameter of 10 cm to prepare a test piece, and this was subjected to a wear test using a Taber abrasion tester (manufactured by Toyo Seiki Co., Ltd.). The test condition is to compare the weight before and after the test after 1000 rotations with no load (wear wheel's own weight) using wear wheel CS-10F in an atmosphere of temperature 23 ° C and relative humidity 50%. It was measured by. The smaller the amount of wear, the better the wear resistance (unit: mg). The results are shown in Tables 1 and 7.

(Print life test)
A pre-prepared photosensitive drum (described later) is mounted on a commercially available color laser printer (LP3000C manufactured by Epson Corporation), and 24,000 sheets of images are formed in a monochrome (black) mode under a normal temperature and humidity environment. The film thickness of the photosensitive layer before image formation and the film thickness of the photosensitive layer after image formation of 24,000 sheets were measured, and the amount of film reduction per 10,000 sheets of image formation was calculated. The smaller the amount of film loss, the better the printing durability (unit: μm). The results are shown in Table 2.

(Preparation of photoreceptor sheet)
10 parts by weight of oxytitanium phthalocyanine and 150 parts by weight of 4-methoxy-4-methylpentanone-2 were mixed and pulverized and dispersed in a sand grind mill to produce a pigment dispersion. Oxytitanium phthalocyanine has Bragg angles (2θ ± 0.2) of 9.3 °, 10.6 °, 13.2 °, 15.1 °, 15.7 °, 16.5 ° in X-ray diffraction by CuKα ray. Strong diffraction peaks are shown at 1 °, 20.8 °, 23.3 °, 26.3 °, and 27.1 °. In this pigment dispersion, 50 parts by weight of a 1,2-dimethoxyethane solution containing 5% by weight of polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka Butyral # 6000C), phenoxy resin (trade name of Union Carbide) PKHH) is mixed with 50 parts by weight of a 1,2-dimethoxyethane solution containing 5% by weight, and then an appropriate amount of 1,2-dimethoxyethane is added to form a coating solution for forming a charge generation layer having a solid concentration of 4.0%. Was prepared. This charge generation layer forming coating solution was applied on a polyethylene terephthalate sheet having aluminum deposited on the surface so that the film thickness after drying was 0.4 μm and dried to provide a charge generation layer.

  Next, a coating solution for forming a charge transport layer is applied onto the charge generation layer so that the film thickness after drying is 20 μm, and dried at 125 ° C. for 20 minutes to form a charge transport layer. A body sheet was prepared. The coating liquid for forming the charge transport layer is 100 parts by weight of the polyester resin shown in Tables 1 and 7, 8 parts by weight of the antioxidant (Irganox 1076), 0.03 parts by weight of silicone oil as a leveling agent, and 50 parts by weight of a charge transporting substance composed of an isomer mainly composed of the charge transporting substance (1) having the chemical structure shown in FIG. Prepared.

(Preparation of photosensitive drum)
10 parts of oxytitanium phthalocyanine was added to 150 parts of 1,2-dimethoxyethane, and pulverized and dispersed in a sand grind mill to prepare a pigment dispersion. Oxytitanium phthalocyanine has Bragg angles (2θ ± 0.2) of 9.3 °, 10.6 °, 13.2 °, 15.1 °, 15.7 °, 16.5 ° in X-ray diffraction by CuKα ray. Strong diffraction peaks are shown at 1 °, 20.8 °, 23.3 °, 26.3 °, and 27.1 °. Next, 5 parts of polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name Denkabutyral # 6000C) was dissolved in 95 parts of 1,2-dimethoxyethane to prepare a binder solution (1) having a solid content concentration of 5%. Subsequently, 5 parts of phenoxy resin (trade name PKHH, manufactured by Union Carbide) was dissolved in 95 parts of 1,2-dimethoxyethane to prepare a binder solution (2) having a solid content concentration of 5%. Next, 160 parts of the previously prepared pigment dispersion, 50 parts of the binder solution (1), 50 parts of the binder solution (2), an appropriate amount of 1,2-dimethoxyethane, and an appropriate amount of 4-methoxy-4- Methylpentanone-2 was added, and the charge generation layer dispersion (α) having a solid content of 4.0% and 1,2-dimethoxyethane: 4-methoxy-4-methylpentanone-2 = 9: 1 Was prepared.

  Next, the surface of a cylinder made of an aluminum alloy having an outer diameter of 30 mm, a length of 285 mm, and a wall thickness of 1.0 mm is mirror-finished and then anodized, followed by a sealant mainly composed of nickel acetate. By performing sealing treatment, an anodic oxide coating (alumite coating) of about 6 μm was formed. This cylinder was dip-coated in the previously prepared dispersion (α) for charge generation layer, and a charge generation layer was formed so that the film thickness after drying was about 0.3 μm. Next, the cylinder on which the charge generation layer was formed was dip-coated in a charge transport layer forming coating solution to prepare a photosensitive drum provided with a charge transport layer having a thickness of 20 μm after drying. The charge transport layer forming coating solution comprises 100 parts of a polyester resin shown in Table 2 as a charge transport layer binder resin, 0.05 part of silicone oil (trade name KF96, manufactured by Shin-Etsu Chemical Co., Ltd.), and the charge transport described above. 50 parts of the substance (1) was dissolved in a mixed solvent of tetrahydrofuran and toluene (tetrahydrofuran 80 wt%, toluene 20 wt%).

(Production example of polyester resin)
Twenty-five types of polyester resins (resin A to resin Y) were prepared by the following production method.

Production Example 1 (Resin A)
In a 1000 mL beaker, 23.02 g of sodium hydroxide and 940 mL of water were weighed and dissolved while stirring. Then, 49.55 g of bis (4-hydroxy-3-methylphenyl) methane (hereinafter referred to as BP-a) was added, stirred and dissolved, and then this aqueous alkaline solution was transferred to a 2 L reaction vessel. Next, 0.5749 g of benzyltriethylammonium chloride and 1.0935 g of 2,3,5-trimethylphenol were sequentially added to the reaction vessel. Next, a mixed solution of 65.29 g of diphenyl ether-4,4′-dicarboxylic acid chloride and 470 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 5 hours, 783 mL of dichloromethane was added and stirring was continued for 7 hours. Thereafter, 8.35 mL of acetic acid was added and stirred for 30 minutes, and then the stirring was stopped and the organic layer was separated. This organic layer was washed twice with 942 mL of a 0.1N aqueous sodium hydroxide solution, then washed twice with 942 mL of 0.1N hydrochloric acid, and further washed twice with 942 mL of water. The washed organic layer was poured into 6266 mL of methanol, and the resulting precipitate was removed by filtration and dried to obtain Resin A. The repeating structure of Resin A is shown below.

Production Example 2 (Resin B)
In a 1000 mL beaker, 26.01 g of sodium hydroxide and 846 mL of water were weighed and dissolved while stirring. (BP-a) 56.00g was added there, and it stirred and melt | dissolved, Then, this alkaline aqueous solution was moved to 2 L reaction tank. Subsequently, 0.6497 g of benzyltriethylammonium chloride and 1.2358 g of 2,3,5-trimethylphenol were sequentially added to the reaction vessel. Separately, a mixed solution of 50.78 g of terephthalic acid chloride and 423 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. As the polymerization progressed, insoluble components appeared in the organic layer, and removal and purification of Resin B were impossible. The repeating structure of Resin B is shown below.

Production Example 3 (Resin C)
In a 500 mL beaker, 10.81 g of sodium hydroxide and 423 mL of water were weighed and dissolved while stirring. (BP-a) 6.98 g and bis (4-hydroxyphenyl) methane (hereinafter BP-b), (2-hydroxyphenyl) (4-hydroxyphenyl) methane (hereinafter BP-c), bis 14.28 g of a mixture of (2-hydroxyphenyl) methane (hereinafter referred to as BP-d) (mixing ratio, BP-b: BP-c: BP-d = about 35:48:17 (hereinafter referred to as BP-e) was added. After stirring and dissolving, the aqueous alkaline solution was transferred to a 1 L reaction vessel, and then 0.2699 g of benzyltriethylammonium chloride and 0.5662 g of p- (tert-butyl) phenol were sequentially added to the reaction vessel. A mixed solution of 30.65 g of -4,4'-dicarboxylic acid chloride and 211 mL of dichloromethane was transferred into the dropping funnel. While maintaining the temperature at 20 ° C., the dichloromethane solution was added dropwise from the dropping funnel over 1 hour while stirring the alkaline aqueous solution in the reaction vessel, and further stirring was continued for 5 hours, and then 352 mL of dichloromethane was added and stirring was continued for 7 hours. Then, 3.92 mL of acetic acid was added and stirred for 30 minutes, and then the stirring was stopped and the organic layer was separated.The organic layer was washed twice with 424 mL of 0.1N aqueous sodium hydroxide solution, and then washed with 0.1N hydrochloric acid. Washing was performed twice with 424 mL, and further with 424 mL of water, and the washed organic layer was poured into 2820 mL of methanol, and the resulting precipitate was filtered out and dried to obtain Resin C. The repeating structure of Resin C is shown below.

Production Example 4 (Resin D)
In a 1000 mL beaker, 27.55 g of sodium hydroxide and 846 mL of water were weighed and dissolved while stirring. (BP-a) 18.03g and (BP-e) 36.91g were added there, and it stirred and melt | dissolved, Then, this alkaline aqueous solution was moved to the 2L reaction tank. Next, 0.6792 g of benzyltriethylammonium chloride and 0.3585 g of 2,3,6-trimethylphenol were sequentially added to the reaction vessel. Separately, a mixed solution of 53.78 g of terephthalic acid chloride and 423 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 5 hours, 705 mL of dichloromethane was added and stirring was continued for 5 hours. Then, after adding 9.99 mL of acetic acid and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 848 mL of a 0.1N aqueous sodium hydroxide solution, then washed twice with 848 mL of 0.1N hydrochloric acid, and further washed twice with 848 mL of water. The washed organic layer was poured into 5639 mL of methanol, and the resulting precipitate was removed by filtration and dried to obtain Resin D. The repeating structure of Resin D is shown below.

Production Example 5 (Resin E)
In a 500 mL beaker, 10.54 g of sodium hydroxide and 423 mL of water were weighed and dissolved while stirring. Thereto, 15.88 g of (BP-a) and 6.03 g of bis (4-hydroxyphenyl) ether (hereinafter referred to as BP-f) were added, stirred and dissolved, and then the aqueous alkaline solution was transferred to a 1 L reaction vessel. Next, 0.2632 g of benzyltriethylammonium chloride and 0.5006 g of 2,3,5-trimethylphenol were sequentially added to the reaction vessel. Separately, a mixed solution of 29.89 g of diphenyl ether-4,4′-dicarboxylic acid chloride and 211 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 5 hours, 352 mL of dichloromethane was added and stirring was continued for 7 hours. Then, after adding 3.82 mL of acetic acid and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 424 mL of 0.1N sodium hydroxide aqueous solution, then washed twice with 424 mL of 0.1N hydrochloric acid, and further washed twice with 424 mL of water. The washed organic layer was poured into 2820 mL of methanol, and the resulting precipitate was filtered out and dried to obtain Resin E. The repeating structure of Resin E is shown below.

Production Example 6 (Resin F)
In a 500 mL beaker, 10.70 g of sodium hydroxide and 423 mL of water were weighed and dissolved while stirring. Then, 14.15 g of (BP-b) and 7.34 g of 1,1-bis (4-hydroxy-3-methylphenyl) ethane (hereinafter referred to as BP-g) were added, stirred and dissolved, and this aqueous alkaline solution was added. Was transferred to a 1 L reactor. Next, 0.2674 g of benzyltriethylammonium chloride and 0.5609 g of p- (tert-butyl) phenol were sequentially added to the reaction vessel. Separately, a mixed solution of 30.36 g of diphenyl ether-4,4′-dicarboxylic acid chloride and 211 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 5 hours, 352 mL of dichloromethane was added and stirring was continued for 7 hours. Then, 3.88 mL of acetic acid was added and stirred for 30 minutes, and then stirring was stopped and the organic layer was separated. This organic layer was washed twice with 424 mL of 0.1N sodium hydroxide aqueous solution, then washed twice with 424 mL of 0.1N hydrochloric acid, and further washed twice with 424 mL of water. The washed organic layer was poured into 2820 mL of methanol, and the resulting precipitate was removed by filtration and dried to obtain Resin F. The repeating structure of Resin F is shown below.

Production Example 7 (Resin G)
In a 1000 mL beaker, 24.64 g of sodium hydroxide and 940 mL of water were weighed and dissolved while stirring. Then, 47.26 g of a mixture of (BP-b) and (BP-c) (mixing ratio, BP-b: BP-c = about 40:60 (hereinafter, BP-h)) was added, stirred and dissolved. Thereafter, this alkaline aqueous solution was transferred to a 2 L reaction vessel. Next, 0.6059 g of benzyltriethylammonium chloride and 0.1772 g of p- (tert-butyl) phenol were sequentially added to the reaction vessel. Separately, a mixed solution of 69.54 g of diphenyl ether-4,4′-dicarboxylic acid chloride and 470 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 5 hours, 783 mL of dichloromethane was added and stirring was continued for 7 hours. Thereafter, 8.93 mL of acetic acid was added and stirred for 30 minutes, and then stirring was stopped and the organic layer was separated. This organic layer was washed twice with 942 mL of a 0.1N aqueous sodium hydroxide solution, then washed twice with 942 mL of 0.1N hydrochloric acid, and further washed twice with 942 mL of water. The washed organic layer was poured into 6266 mL of methanol, and the resulting precipitate was removed by filtration and dried to obtain Resin G. The repeating structure of the resin G is shown below.

Production Example 8 (Resin H)
In a 1000 mL beaker, 28.12 g of sodium hydroxide and 846 mL of water were weighed and dissolved while stirring. (BP-h) 53.10g was added there, and it stirred and melt | dissolved, Then, this alkaline aqueous solution was moved to 2 L reaction tank. Next, 0.7024 g of benzyltriethylammonium chloride and 1.4736 g of p- (tert-butyl) phenol were sequentially added to the reaction vessel. Separately, a mixed solution of 54.90 g of terephthalic acid chloride and 423 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 5 hours, 705 mL of dichloromethane was added and stirring was continued for 2 hours. Then, after adding 10.20 mL of acetic acid and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 848 mL of a 0.1N aqueous sodium hydroxide solution, then washed twice with 848 mL of 0.1N hydrochloric acid, and further washed twice with 848 mL of water. The washed organic layer was poured into 5639 mL of methanol, and the resulting precipitate was removed by filtration and dried to obtain Resin H. The repeating structure of the resin H is shown below.

Production Example 9 (Resin I)
In a 500 mL beaker, 10.31 g of sodium hydroxide and 423 mL of water were weighed and dissolved while stirring. (BP-g) 16.49g and (BP-f) 5.90g were added there, and it stirred and melt | dissolved, Then, this alkaline aqueous solution was moved to 1L reaction tank. Next, 0.2576 g of benzyltriethylammonium chloride and 0.4900 g of 2,3,5-trimethylphenol were sequentially added to the reaction vessel. Separately, a mixed solution of 29.26 g of diphenyl ether-4,4′-dicarboxylic acid chloride and 211 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 5 hours, 352 mL of dichloromethane was added and stirring was continued for 7 hours. Thereafter, 3.74 mL of acetic acid was added and stirred for 30 minutes, and then stirring was stopped and the organic layer was separated. This organic layer was washed twice with 424 mL of 0.1N sodium hydroxide aqueous solution, then washed twice with 424 mL of 0.1N hydrochloric acid, and further washed twice with 424 mL of water. A precipitate obtained by pouring the washed organic layer into 2820 mL of methanol was taken out by filtration and dried to obtain Resin I. The repeating structure of Resin I is shown below.

Production Example 10 (Resin J)
In a 1000 mL beaker, 22.34 g of sodium hydroxide and 940 mL of water were weighed and dissolved while stirring. (BP-g) 51.04g was added there, and it stirred and melt | dissolved, Then, this alkaline aqueous solution was moved to the 2L reaction tank. Next, 0.5579 g of benzyltriethylammonium chloride and 1.0613 g of 2,3,5-trimethylphenol were sequentially added to the reaction vessel. Separately, a mixed solution of 63.37 g of diphenyl ether-4,4′-dicarboxylic acid chloride and 470 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 5 hours, 783 mL of dichloromethane was added and stirring was continued for 7 hours. Thereafter, 8.10 mL of acetic acid was added and stirred for 30 minutes, then stirring was stopped and the organic layer was separated. This organic layer was washed twice with 942 mL of a 0.1N aqueous sodium hydroxide solution, then washed twice with 942 mL of 0.1N hydrochloric acid, and further washed twice with 942 mL of water. The washed organic layer was poured into 6266 mL of methanol and the resulting precipitate was filtered out and dried to obtain Resin J. The repeating structure of Resin J is shown below.

Production Example 11 (Resin K)
In a 1000 mL beaker, 23.71 g of sodium hydroxide and 940 mL of water were weighed and dissolved while stirring. Thereto was added 47.91 g of 1,1-bis (4-hydroxyphenyl) ethane (hereinafter referred to as BP-i), stirred and dissolved, and then the alkaline aqueous solution was transferred to a 2 L reaction vessel. Subsequently, 0.5923 g of benzyltriethylammonium chloride and 1.2425 g of p- (tert-butyl) phenol were sequentially added to the reaction vessel. Separately, a mixed solution of 67.27 g of diphenyl ether-4,4′-dicarboxylic acid chloride and 470 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 5 hours, 783 mL of dichloromethane was added and stirring was continued for 7 hours. Thereafter, 8.60 mL of acetic acid was added and stirred for 30 minutes, and then stirring was stopped and the organic layer was separated. This organic layer was washed twice with 942 mL of a 0.1N aqueous sodium hydroxide solution, then washed twice with 942 mL of 0.1N hydrochloric acid, and further washed twice with 942 mL of water. The washed organic layer was poured into 6266 mL of methanol, and the resulting precipitate was removed by filtration and dried to obtain Resin K. The repeating structure of resin K is shown below.

Production Example 12 (Resin L)
In a 500 mL beaker, 13.52 g of sodium hydroxide and 423 mL of water were weighed and dissolved while stirring. 27.32 g of (BP-i) was added, stirred and dissolved therein, and then this alkaline aqueous solution was transferred to a 1 L reaction vessel. Next, 0.3378 g of benzyltriethylammonium chloride and 0.6425 g of 2,3,6-trimethylphenol were sequentially added to the reaction vessel. Separately, a mixed solution of 26.40 g of terephthalic acid chloride and 211 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. As the polymerization progressed, insoluble components appeared in the organic layer, and removal and purification of the resin L were impossible. The repeating structure of the resin L is shown below.

Production Example 13 (Resin M)
In a 1000 mL beaker, 25.06 g of sodium hydroxide and 846 mL of water were weighed and dissolved while stirring. (BP-g) 57.25g was added there, and it stirred and melt | dissolved, Then, this alkaline aqueous solution was moved to 2 L reaction tank. Next, 0.6258 g of benzyltriethylammonium chloride and 1.1904 g of 2,3,6-trimethylphenol were sequentially added to the reaction vessel. Separately, a mixed solution of 48.91 g of terephthalic acid chloride and 423 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 5 hours, 705 mL of dichloromethane was added and stirring was continued for 2 hours. Then, after 9.09 mL of acetic acid was added and stirred for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 848 mL of a 0.1N aqueous sodium hydroxide solution, then washed twice with 848 mL of 0.1N hydrochloric acid, and further washed twice with 848 mL of water. The washed organic layer was poured into 5639 mL of methanol, and the resulting precipitate was removed by filtration and dried to obtain Resin M. The repeating structure of the resin M is shown below.

Production Example 14 (Resin N)
In a 500 mL beaker, 10.85 g of sodium hydroxide and 470 mL of water were weighed and dissolved while stirring. Thereto, 26.22 g of bis (4-hydroxy-3,5-dimethylphenyl) methane (hereinafter referred to as BP-j) was added, stirred and dissolved, and then this aqueous alkaline solution was transferred to a 1 L reaction vessel. Next, 0.2710 g of benzyltriethylammonium chloride and 0.5154 g of 2,3,6-trimethylphenol were sequentially added to the reaction vessel. Separately, a mixed solution of 30.77 g of diphenyl ether-4,4′-dicarboxylic acid chloride and 235 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 5 hours, 392 mL of dichloromethane was added and stirring was continued for 7 hours. Then, after adding 3.93 mL of acetic acid and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 471 mL of a 0.1N aqueous sodium hydroxide solution, then washed twice with 471 mL of 0.1N hydrochloric acid, and further washed twice with 471 mL of water. The washed organic layer was poured into 3133 mL of methanol and the resulting precipitate was filtered out and dried to obtain Resin N. The repeating structure of the resin N is shown below.

Production Example 15 (Resin O)
In a 1000 mL beaker, 7.25 g of sodium hydroxide and 600 mL of water were weighed and dissolved while stirring. Thereto, 17.39 g of (BP-j) was added, stirred and dissolved, and then this alkaline aqueous solution was transferred to a 1 L reaction vessel. Subsequently, 0.0912 g of benzyltriethylammonium chloride and 0.4822 g of 2,4,6-trimethylphenol were sequentially added to the reaction vessel. Separately, a mixed solution of 14.15 g of terephthalic acid chloride and 300 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour, and stirring was continued for 5 hours. Thereafter, 2.39 mL of acetic acid was added and stirred for 30 minutes, and then the stirring was stopped and the organic layer was separated. This organic layer was washed twice with 339 mL of a 0.1N aqueous sodium hydroxide solution, then washed twice with 339 mL of 0.1N hydrochloric acid, and further washed twice with 339 mL of water. The washed organic layer was poured into 1500 mL of methanol, and the resulting precipitate was filtered out and dried to obtain resin O. The repeating structure of the resin O is shown below.

Production Example 16 (Resin P)
In a 500 mL beaker, 9.52 g of sodium hydroxide and 470 mL of water were weighed and dissolved while stirring. 29.13 g of 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane (hereinafter referred to as BP-k) was added, stirred and dissolved therein, and the aqueous alkaline solution was transferred to a 1 L reaction vessel. Next, 0.2378 g of benzyltriethylammonium chloride and 0.4524 g of 2,3,6-trimethylphenol were sequentially added to the reaction vessel. Separately, a mixed solution of 27.01 g of diphenyl ether-4,4′-dicarboxylic acid chloride and 235 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 5 hours, 392 mL of dichloromethane was added and stirring was continued for 7 hours. Then, 3.45 mL of acetic acid was added and stirred for 30 minutes, and then stirring was stopped and the organic layer was separated. This organic layer was washed twice with 471 mL of a 0.1N aqueous sodium hydroxide solution, then washed twice with 471 mL of 0.1N hydrochloric acid, and further washed twice with 471 mL of water. The washed organic layer was poured into 3133 mL of methanol, and the resulting precipitate was removed by filtration and dried to obtain Resin P. The repeating structure of the resin P is shown below.

Production Example 17 (Resin Q)
In a 500 mL beaker, 6.60 g of sodium hydroxide and 281 mL of water were weighed and dissolved while stirring. Then, 17.65 g of (BP-k) was added, stirred and dissolved, and then this aqueous alkaline solution was transferred to a 1 L reaction vessel. Next, 0.0709 g of benzyltriethylammonium chloride and 0.1481 g of 2,3,6-trimethylphenol were sequentially added to the reaction vessel. Separately, a mixed solution of 11.17 g of terephthalic acid chloride and 281 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour, and stirring was continued for 6 hours. Thereafter, 3.46 mL of acetic acid was added and stirred for 30 minutes, and then the stirring was stopped and the organic layer was separated. This organic layer was washed twice with 313 mL of a 0.1N aqueous sodium hydroxide solution, then washed twice with 313 mL of 0.1N hydrochloric acid, and further washed twice with 313 mL of water. The washed organic layer was poured into 1403 mL of methanol, and the resulting precipitate was removed by filtration and dried to obtain Resin Q. The repeating structure of the resin Q is shown below.

Production Example 18 (Resin R)
In a 500 mL beaker, 13.29 g of sodium hydroxide and 423 mL of water were weighed and dissolved while stirring. (BP-f) 7.60g and (BP-a) 20.02g were added there, and it stirred and melt | dissolved, Then, this alkaline aqueous solution was moved to 1L reaction tank. Subsequently, 0.3319 g of benzyltriethylammonium chloride and 0.6314 g of 2,3,5-trimethylphenol were sequentially added to the reaction vessel. Separately, a mixed solution of 25.94 g of terephthalic acid chloride and 211 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. As the polymerization progressed, insoluble components appeared in the organic layer, and removal and purification of the resin R were impossible. The repeating structure of the resin R is shown below.

Production Example 19 (Resin S)
In a 500 mL beaker, 12.94 g of sodium hydroxide and 423 mL of water were weighed and dissolved while stirring. (BP-f) 7.40g and (BP-g) 20.69g were added there, and it stirred and melt | dissolved, Then, this alkaline aqueous solution was moved to 1L reaction tank. Next, 0.3231 g of benzyltriethylammonium chloride and 0.6146 g of 2,3,5-trimethylphenol were sequentially added to the reaction vessel. Separately, a mixed solution of 25.25 g of terephthalic acid chloride and 211 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. As the polymerization progressed, insoluble components appeared in the organic layer, and removal and purification of the resin S were impossible. The repeating structure of the resin S is shown below.

Production Example 20 (Resin T)
In a 1000 mL beaker, 21.70 g of sodium hydroxide and 940 mL of water were weighed and dissolved while stirring. Thereto, 52.44 g of 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter referred to as BP-1) was added, stirred and dissolved, and then the aqueous alkaline solution was transferred to a 2 L reaction vessel. Next, 0.5419 g of benzyltriethylammonium chloride and 1.0308 g of 2,3,5-trimethylphenol were sequentially added to the reaction vessel.
Separately, a mixed solution of 61.55 g of diphenyl ether-4,4′-dicarboxylic acid chloride and 470 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 5 hours, 783 mL of dichloromethane was added and stirring was continued for 7 hours. Thereafter, 7.87 mL of acetic acid was added and stirred for 30 minutes, and then the stirring was stopped and the organic layer was separated. This organic layer was washed twice with 942 mL of a 0.1N aqueous sodium hydroxide solution, then washed twice with 942 mL of 0.1N hydrochloric acid, and further washed twice with 942 mL of water. The washed organic layer was poured into 6266 mL of methanol, and the resulting precipitate was removed by filtration and dried to obtain Resin T. The repeating structure of the resin T is shown below.

Production Example 21 (Resin U)
In a 500 mL beaker, 12.08 g of sodium hydroxide and 423 mL of water were weighed and dissolved while stirring. (BP-1) 29.20g was added there, and it stirred and melt | dissolved, Then, this alkaline aqueous solution was moved to 1 L reaction tank. Next, 0.3018 g of benzyltriethylammonium chloride and 0.5741 g of 2,3,6-trimethylphenol were sequentially added to the reaction vessel. Separately, a mixed solution of 23.59 g of terephthalic acid chloride and 211 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 5 hours, 352 mL of dichloromethane was added and stirring was continued for 2 hours. Thereafter, 4.38 mL of acetic acid was added and stirred for 30 minutes, and then the stirring was stopped and the organic layer was separated. This organic layer was washed twice with 424 mL of 0.1N sodium hydroxide aqueous solution, then washed twice with 424 mL of 0.1N hydrochloric acid, and further washed twice with 424 mL of water. The washed organic layer was poured into 2820 mL of methanol, and the resulting precipitate was removed by filtration and dried to obtain Resin U. The repeating structure of the resin U is shown below.

Production Example 22 (Resin V)
In a 500 mL beaker, 10.58 g of sodium hydroxide and 470 mL of water were weighed and dissolved while stirring. Then, 26.76 g of 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter referred to as BP-m) was added, stirred and dissolved, and then the aqueous alkaline solution was transferred to a 1 L reaction vessel. Next, 0.2642 g of benzyltriethylammonium chloride and 0.5543 g of p- (tert-butyl) phenol were sequentially added to the reaction vessel. Separately, a mixed solution of 30.01 g of diphenyl ether-4,4′-dicarboxylic acid chloride and 235 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 5 hours, 392 mL of dichloromethane was added and stirring was continued for 7 hours. Then, after adding 3.84 mL of acetic acid and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 471 mL of a 0.1N aqueous sodium hydroxide solution, then washed twice with 471 mL of 0.1N hydrochloric acid, and further washed twice with 471 mL of water. The washed organic layer was poured into 3133 mL of methanol and the resulting precipitate was filtered out and dried to obtain Resin V. The repeating structure of Resin V is shown below.

Production Example 23 (Resin W)
In a 500 mL beaker, 4.62 g of sodium hydroxide and 400 mL of water were weighed and dissolved while stirring. After adding 11.70 g of (BP-m) there, stirring, and melt | dissolving, this alkaline aqueous solution was moved to 1 L reaction tank. Next, 0.0583 g of benzyltriethylammonium chloride and 0.1987 g of p- (tert-butyl) phenol were sequentially added to the reaction vessel. Separately, a mixed solution of 9.46 g of terephthalic acid chloride and 200 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. As the polymerization progressed, insoluble components appeared in the organic layer, and removal and purification of the resin W were impossible. The repeating structure of the resin W is shown below.

Production Example 24 (Resin X)
In a 1000 mL beaker, 22.99 g of sodium hydroxide and 940 mL of water were weighed and dissolved while stirring. 49.49 g of 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as BP-n) was added, stirred and dissolved therein, and the aqueous alkaline solution was transferred to a 2 L reaction vessel. Next, 0.5743 g of benzyltriethylammonium chloride and 1.2048 g of p- (tert-butyl) phenol were sequentially added to the reaction vessel. Separately, a mixed solution of 65.22 g of diphenyl ether-4,4′-dicarboxylic acid chloride and 470 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 5 hours, 783 mL of dichloromethane was added and stirring was continued for 7 hours. Thereafter, 8.34 mL of acetic acid was added and stirred for 30 minutes, and then the stirring was stopped and the organic layer was separated. This organic layer was washed twice with 942 mL of a 0.1N aqueous sodium hydroxide solution, then washed twice with 942 mL of 0.1N hydrochloric acid, and further washed twice with 942 mL of water. The washed organic layer was poured into 6266 mL of methanol, and the resulting precipitate was removed by filtration and dried to obtain Resin X. The repeating structure of Resin X is shown below.

Production Example 25 (Resin Y)
In a 500 mL beaker, 14.43 g of sodium hydroxide and 470 mL of water were weighed and dissolved while stirring. (BP-n) 31.06g was added there, and it stirred and melt | dissolved, Then, this alkaline aqueous solution was moved to 1 L reaction tank. Subsequently, 0.3605 g of benzyltriethylammonium chloride and 0.7562 g of p- (tert-butyl) phenol were sequentially added to the reaction vessel. Separately, a mixed solution of 28.17 g of terephthalic acid chloride and 235 mL of dichloromethane was transferred into the dropping funnel. While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. As the polymerization progressed, insoluble components appeared in the organic layer, and removal and purification of the resin Y were impossible. The repeating structure of Resin Y is shown below.

(Example 1 to Example 10, Comparative Example 1 to Comparative Example 8)
The photoreceptor sheets prepared using the polyester resins as shown in Table 1 were subjected to electrical characteristics and an abrasion test. The results are shown in Table 1.

The compounds indicated by abbreviations in Table 1 are as follows.
ODBA: diphenyl ether-4,4′-dicarboxylic acid residue TPA: terephthalic acid residue BP-a: bis (4-hydroxy-3-methylphenyl) methane BP-b: bis (4-hydroxyphenyl) methane BP-e : Bis (4-hydroxyphenyl) methane: (2-hydroxyphenyl) (4-hydroxyphenyl) methane: bis (2-hydroxyphenyl) methane = about 35:48:17 mixture BP-f: bis (4-hydroxyphenyl) ) Ether BP-g: 1,1-bis (4-hydroxy-3-methylphenyl) ethane BP-j: bis (4-hydroxy-3,5-dimethylphenyl) methane BP-k: 1,1-bis ( 4-hydroxy-3,5-dimethylphenyl) cyclohexane BP-1: 2,2-bis (4-hydroxy-3-methylpheny) E) Propane BP-m: 1,1-bis (4-hydroxyphenyl) cyclohexane

From the results shown in Table 1, polyester having diphenyl ether-4,4′-dicarboxylic acid residue (ODBA) in the molecule and having a repeating structure represented by the general formulas (1) to (5) described above. The resin exhibits high solubility and coating solution stability with respect to a solvent usually used in a coating solution for forming a charge transport layer, and a photoreceptor sheet provided with a photosensitive layer containing at least one of these polyester resins (Examples) 1 to 10) it can be seen that good performance is obtained in electrical properties and wear tests.
On the other hand, some polyester resins having a terephthalic acid residue (TPA) in the molecule are insoluble in the solvent used for the charge transport layer forming coating solution (resin B, resin R, resin S, resin W). The photoreceptor sheet cannot be prepared. In addition, the photosensitive sheet (Comparative Example 2, Comparative Example 3, Comparative Example 4, and Comparative Example 7) provided with a photosensitive layer containing these polyester resins cannot obtain sufficient performance in electrical characteristics and wear tests. I understand.

(Example 11 to Example 17, Comparative Example 9 to Comparative Example 13)
A printing durability test was conducted on the photosensitive drums prepared using the polyester resins as shown in Table 2. The results are shown in Table 2.

The compounds shown in abbreviations in Table 2 are as follows.
ODBA: diphenyl ether-4,4′-dicarboxylic acid residue TPA: terephthalic acid residue BP-a: bis (4-hydroxy-3-methylphenyl) methane BP-e: bis (4-hydroxyphenyl) methane: (2 -Hydroxyphenyl) (4-hydroxyphenyl) methane: bis (2-hydroxyphenyl) methane = about 35:48:17 mixture BP-g: 1,1-bis (4-hydroxy-3-methylphenyl) ethane BP- h: bis (4-hydroxyphenyl) methane: (2-hydroxyphenyl) (4-hydroxyphenyl) methane = about 40:60 mixture BP-i: 1,1-bis (4-hydroxyphenyl) ethane BP-1: 2,2-bis (4-hydroxy-3-methylphenyl) propane BP-n: 2,2-bis (4-hydroxyphenyl) )propane

From the results shown in Table 2, the polyester having a diphenyl ether-4,4′-dicarboxylic acid residue (ODBA) in the molecule and having a repeating structure represented by the general formulas (1) to (5) described above. It can be seen that the photosensitive drum (Examples 11 to 17) provided with the photosensitive layer containing at least one resin can obtain good performance in the printing durability test.
In contrast, some polyester resins having a terephthalic acid residue (TPA) in the molecule are insoluble in the solvent used in the coating solution for forming the charge transport layer (resin B, resin L, resin Y), and photoconductor. The drum cannot be prepared. It can also be seen that the photosensitive drums (Comparative Example 10 and Comparative Example 12) provided with a photosensitive layer containing these polyester resins cannot obtain sufficient performance in the printing durability test.

  Further, with respect to the photosensitive drum J2 and the photosensitive drum M2 manufactured as Example 14 and Comparative Example 12, in order to create a portion exposed to light of a white fluorescent lamp and a portion not exposed to light on the photosensitive drum. Cover the entire surface of the photoconductor with black paper with a hole of 20 mm and 40 mm in width, and then apply the light from the white fluorescent lamp (“Neormi Super FL20SS / W / 18” manufactured by Mitsubishi OSRAM Co., Ltd.) to the surface of the photoconductor After adjusting the light intensity at 2000 lux to irradiate for 10 minutes around the black paper hole, remove the black paper, attach the drum to the electrical property tester, and expose to light. The potential difference between the part and the unexposed part was measured. The results are shown in Table 3.

  From the results in Table 3, it can be seen that the photoreceptor J2 of Example 14 also has light resistance, which is an important characteristic as an electrophotographic photoreceptor. On the other hand, it can be seen that the photoconductor M2 of Comparative Example 12 shows a good film reduction amount in the printing durability test, but has very low light resistance and cannot withstand actual use.

Moreover, five types of polyester resins (resin JA to resin JE) were manufactured by the following manufacturing method.
Production Example 26 (Resin JA)
Sodium hydroxide (10.15 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-g (23.01 g) was added, stirred and dissolved therein, and then the aqueous alkaline solution was transferred to a 1 L reaction vessel. Benzyltriethylammonium chloride (0.2552 g) and 2,3,5-trimethylphenol (0.6725 g) were then sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.20 g) and dichloromethane (211 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.68 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further washed with H ₂ O (424 mL). We went twice. The target solvent JA was obtained by removing the organic solvent from the organic layer. The obtained resin JA had a viscosity average molecular weight of 41,000. In addition, since the repeating structure of the resin JA is the same as that of the resin J obtained in Production Example 10, the description is omitted.

Production Example 27 (Resin JB)
Sodium hydroxide (10.14 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. After adding BP-g (22.75g) there, stirring and melt | dissolving, this alkaline aqueous solution was moved to 1 L reaction tank. Benzyltriethylammonium chloride (0.2576 g) and 2,3,5-trimethylphenol (0.9462 g) were then sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.19 g) and dichloromethane (211 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.68 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then twice with 0.1N hydrochloric acid (424 mL), and further washed with H ₂ O (424 mL). It went twice. The washed organic layer was poured into methanol (2820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin JB. The obtained resin JB had a viscosity average molecular weight of 31,500. Note that the repeating structure of the resin JB is the same as that of the resin J obtained in Production Example 10, and thus the description thereof is omitted.

Production Example 28 (Resin JC)
Sodium hydroxide (10.14 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. After adding BP-g (22.75g) there, stirring and melt | dissolving, this alkaline aqueous solution was moved to 1 L reaction tank. Benzyltriethylammonium chloride (0.2576 g) and 2,3,5-trimethylphenol (0.9462 g) were then sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.19 g) and dichloromethane (211 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, after adding acetic acid (3.68 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then washed four times with 0.1N hydrochloric acid (424 mL), and further washed with H ₂ O (424 mL). It went twice. The target solvent JC was obtained by removing the organic solvent from the organic layer. The obtained resin JC had a viscosity average molecular weight of 31,500. In addition, since the repeating structure of the resin JC is the same as that of the resin J obtained in Production Example 10, the description thereof is omitted.

Production Example 29 (Resin JD)
Sodium hydroxide (10.15 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-g (23.01 g) was added, stirred and dissolved therein, and then the aqueous alkaline solution was transferred to a 1 L reaction vessel. Benzyltriethylammonium chloride (0.2552 g) and 2,3,5-trimethylphenol (0.6725 g) were then sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.20 g) and dichloromethane (211 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, stirring was stopped and the organic layer was separated. This organic layer was washed 4 times with 0.1N hydrochloric acid (424 mL), and further washed twice with H ₂ O (424 mL). The target solvent JD was obtained by removing the organic solvent from the organic layer. The viscosity average molecular weight of the obtained resin JD was 41,000. In addition, since the repeating structure of the resin JD is the same as the resin J obtained in the manufacture example 10, it abbreviate | omits.

Production Example 30 (Resin JE)
Sodium hydroxide (10.14 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. After adding BP-g (22.75g) there, stirring and melt | dissolving, this alkaline aqueous solution was moved to 1 L reaction tank. Benzyltriethylammonium chloride (0.2576 g) and 2,3,5-trimethylphenol (0.9462 g) were then sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (28.19 g) and dichloromethane (211 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 6 hours. Then, stirring was stopped and the organic layer was separated. This organic layer was washed 4 times with 0.1N hydrochloric acid (424 mL), and further washed twice with H ₂ O (424 mL). The organic solvent in the organic layer was removed to obtain the target resin JE. The obtained resin JE had a viscosity average molecular weight of 31,500. Note that the repeated structure of the resin JE is the same as that of the resin J obtained in Production Example 10 and thus will not be described.

  The undercoat layer dispersion was produced as follows. That is, rutile type titanium oxide having an average primary particle diameter of 40 nm (“TTO55N” manufactured by Ishihara Sangyo Co., Ltd.) and 3% by weight of methyldimethoxysilane (“TSL8117” manufactured by Toshiba Silicone Co., Ltd.) with respect to the titanium oxide, A surface-treated titanium oxide obtained by high-speed fluid mixing and kneading (“SMG300” manufactured by Kawata Co., Ltd.) and high-speed mixing at a rotational peripheral speed of 34.5 m / sec is mixed with methanol / 1-propanol. By dispersing with a ball mill, a hydrophobized titanium oxide dispersion slurry was obtained. The dispersion slurry, a mixed solvent of methanol / 1-propanol / toluene, and ε-caprolactam / bis (4-amino-3-methylcyclohexyl) methane / hexamethylenediamine / decamethylenedicarboxylic acid / octadecamethylenedicarboxylic acid The polyamide pellets were dissolved by stirring and mixing with the copolymerized polyamide pellets having a composition molar ratio of 75% / 9.5% / 3% / 9.5% / 3%, and then subjected to ultrasonic waves. By carrying out the dispersion treatment, the solid content concentration is 18.0 which contains methanol / 1-propanol / toluene in a weight ratio of 7/1/2 and hydrophobically treated titanium oxide / copolymerized polyamide in a weight ratio of 3/1. % Dispersion for undercoat layer.

(Preparation of dispersion for charge generation layer)
10 parts by weight of oxytitanium phthalocyanine, which shows a maximum diffraction peak at a Bragg angle (2θ ± 0.2) of 27.3 ° in X-ray diffraction using CuKα rays, is added to 150 parts by weight of 1,2-dimethoxyethane, and is added to a sand grind mill. The mixture was pulverized and dispersed to prepare a pigment dispersion.
In 160 parts by weight of this pigment dispersion, 5 parts by weight of polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka Butyral # 6000C) was dissolved in 95 parts by weight of 1,2-dimethoxyethane, and the solid content concentration was 5% by weight. 100 parts by weight of the binder solution, an appropriate amount of 1,2-dimethoxyethane and an appropriate amount of 4-methoxy-4-methyl-2-pentanone were added, and the solid content concentration was 4.0% by weight, 1,2-dimethoxyethane: 4- A dispersion β1 for charge generation layer with methoxy-4-methyl-2-pentanone = 9: 1 was prepared.
Bragg angles (2θ ± 0.2) 9.3 °, 10.6 °, 13.2 °, 15.1 °, 15.7 °, 16.1 °, 20.8 ° in X-ray diffraction by CuKα ray , 10 parts by weight of oxytitanium phthalocyanine showing strong diffraction peaks at 23.3 °, 26.3 °, and 27.1 ° are added to 150 parts by weight of 1,2-dimethoxyethane, and pulverized and dispersed in a sand grind mill. And a pigment dispersion was prepared.
In 160 parts by weight of this pigment dispersion, 5 parts by weight of polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka Butyral # 6000C) was dissolved in 95 parts by weight of 1,2-dimethoxyethane, and the solid content concentration was 5% by weight. 100 parts by weight of the binder solution, an appropriate amount of 1,2-dimethoxyethane and an appropriate amount of 4-methoxy-4-methyl-2-pentanone were added, and the solid content concentration was 4.0%, 1,2-dimethoxyethane: 4-methoxy A charge generating layer dispersion β2 of -4-methyl-2-pentanone = 9: 1 was prepared.
Charge generation layer dispersion β1 and charge generation layer dispersion β2 were mixed at a ratio of 8: 2 to prepare charge generation layer dispersion β.

(Production of photoconductor)
Example 18
A cylinder made of an aluminum alloy having an outer diameter of 30 mm, a length of 254 mm, and a wall thickness of 0.75 mm, whose surface is roughly cut (Rmax = 0.8), is dip-coated in the previously prepared dispersion for the undercoat layer to form a film. An undercoat layer having a thickness of about 1.3 μm was formed. This cylinder was dip-coated in the charge generation layer dispersion β prepared above, and a charge generation layer was formed so that the weight after drying was 0.3 g / m 2 (film thickness: about 0.3 μm).
Next, the cylinder in which the charge generation layer is formed is produced in Production Example 7 as 50 parts by weight of the charge transport material composed of the isomer mixture mainly composed of the charge transport material (1) and the binder resin for the charge transport layer. 100 parts by weight of the polyester resin (resin G) and 0.05 parts by weight of silicone oil (trade name KF96, manufactured by Shin-Etsu Chemical Co., Ltd.) are dissolved in 640 parts by weight of a tetrahydrofuran / toluene mixed solvent (80% by weight of tetrahydrofuran, 20% by weight of toluene). A charge transport layer having a film thickness of 25 μm after drying was provided by dip-coating into the liquid. The photosensitive drum thus obtained is designated G3.

Comparative Example 14
A photosensitive drum H3 was produced in the same manner as in Example 18 except that the polyester resin in Production Example 8 was used as the polyester resin (Resin H).

Example 19
Photosensitive drum J3 was produced in the same manner as in Example 18 except that the polyester resin in Production Example 10 was used as the polyester resin.

Example 20
A photosensitive drum K3 was produced in the same manner as in Example 18 except that the polyester resin in Production Example 11 was used as the polyester resin (Resin K).

Comparative Example 15
A photosensitive drum M3 was produced in the same manner as in Example 18 except that the polyester resin in Production Example 13 was used as the polyester resin (Resin M).

  Mount these photoconductors (G3, H3, J3, K3, M3) on a commercially available monochrome laser printer (manufactured by Lexmark, Optra S2450, 24 sheets per minute with A4 vertical feed, DC charged roller charging, roller transfer) Then, 30,000 sheets were printed under normal temperature and humidity. The amount of film reduction per 10,000 sheets was calculated from the difference in film thickness before and after printing. The results are shown in Table 4.

  From the results in Table 4, it can be seen that the amount of wear in the printing durability test of the photoreceptors (G3, J3, K3) is small and the printing durability is good.

Example 21
The surface of a cylinder made of an aluminum alloy having an outer diameter of 30 mm, a length of 346 mm, and a wall thickness of 1.0 mm, whose surface has been roughly cut (Rmax = 1.0), is subjected to anodizing treatment, and then nickel acetate as a main component. By performing sealing treatment with a sealing agent, an anodic oxide coating (alumite coating) of about 6 μm was formed.
This cylinder was dip-coated in the previously prepared dispersion for the undercoat layer to form an undercoat layer having a thickness of about 1.3 μm after drying. Further, the charge generation layer was formed by dip-coating in the charge generation layer dispersion β1 prepared earlier so that the weight after drying was 0.3 g / m 2 (film thickness: about 0.3 μm).
Next, the cylinder in which the charge generation layer is formed is charged with 30 parts by weight of a charge transport material composed of an isomer mixture containing the charge transport material (1) as a main component and 4 weights of an antioxidant (Irganox 1076, manufactured by Ciba Geigy). 100 parts by weight of the polyester resin (resin J) produced in Production Example 10 as a binder resin for the charge transport layer and 0.05 parts by weight of silicone oil (trade name KF96, manufactured by Shin-Etsu Chemical Co., Ltd.) A charge transport layer having a thickness of 25 μm after drying was provided by dip coating in a solution dissolved in 640 parts by weight (80% by weight, 20% by weight of toluene). The photoreceptor drum thus obtained is designated as J4.

Comparative Example 16
A photoconductive drum M4 was produced in the same manner as in Example 21 except that the polyester resin in Production Example 13 was used as the polyester resin (Resin M).

Example 22
Photosensitive drum J4A was produced in the same manner as in Example 21 except that the polyester resin was replaced with a resin JA having a viscosity average molecular weight Mv41,000 comprising the same repeating structural unit as that of resin J.

Example 23
A photosensitive drum J4B was produced in the same manner as in Example 21 except that the polyester resin was replaced with a resin JB having a viscosity average molecular weight Mv31,500 consisting of the same repeating structural unit as that of the resin J.

Comparative Example 17
A photoconductor in the same manner as in Example 21 except that a polycarbonate resin having a repeating unit of bisphenol Z (PCZ-400, viscosity average molecular weight Mv of about 40,000) made of bisphenol Z is used in place of the polyester resin. Drum Z4 was produced.

  These photoconductors (J4, J4A, J4B, M4, Z4) are commercially available digital multifunction machines (manufactured by Panasonic Communications Co., Ltd., WORKIO3200, 32 sheets per minute with A4 lateral feed, roller charging with AC superimposed DC voltage applied, magnetic one component Jumping development, resolution 600 dpi × 600 dpi) was mounted, and 30,000 sheets were printed under normal temperature and humidity. The amount of film reduction per 10,000 sheets was calculated from the difference in film thickness before and after printing. The results are shown in Table 5.

  From the results in Table 5, it can be seen that the wear amount of the photoconductors (J4, J4A, J4B) in the printing durability test is small and the printing durability is good.

Example 24
A cylinder made of an aluminum alloy having an outer diameter of 30 mm, a length of 350 mm, and a wall thickness of 1.0 mm, whose surface was roughly cut (Rmax = 1.2), was dip-coated in the previously prepared dispersion for the undercoat layer. An undercoat layer having a thickness of about 2 μm was formed. This cylinder was dip-coated in the charge generation layer dispersion β1 prepared previously, and a charge generation layer was formed so that the weight after drying was 0.3 g / m 2 (film thickness: about 0.3 μm).
Next, the cylinder in which the charge generation layer is formed is produced in Production Example 1 as 50 parts by weight of a charge transport material composed of an isomer mixture containing the charge transport material (1) as a main component and a binder resin for the charge transport layer. 100 parts by weight of the polyester resin (resin A) and 0.05 parts by weight of silicone oil (trade name KF96, manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 640 parts by weight of a tetrahydrofuran / toluene mixed solvent (tetrahydrofuran 80% by weight, toluene 20% by weight). A charge transport layer having a film thickness of 26 μm after drying was provided by dip-coating into the liquid. The photoreceptor drum thus obtained is designated as A5.

Example 25
A photosensitive drum J5A was produced in the same manner as in Example 24 except that the polyester resin was replaced with a resin JA having a viscosity average molecular weight Mv41,000 comprising the same repeating structural unit as that of the resin J.

Comparative Example 18
A photoconductor in the same manner as in Example 24 except that a polycarbonate resin having a repeating unit of bisphenol Z (PCZ-400, viscosity average molecular weight Mv of about 40,000) made of bisphenol Z is used instead of the polyester resin. Drum Z5 was produced.

Comparative Example 19
A photosensitive drum ZBp5 was produced in the same manner as in Example 24 except that polycarbonate resin ZBp (viscosity average molecular weight Mv: about 40,500) having the following structure was used instead of the polyester resin.

  Mount these photoconductors (A5, J5A, Z5, ZBp5) on a commercially available digital multifunction machine (Minolta, DiALTA Di350, 35 sheets per minute with A4 horizontal feed, scorotron charging, two-component development, resolution 600 dpi x 600 dpi) Then, 50,000 sheets were printed under normal temperature and humidity. The amount of film reduction per 10,000 sheets was calculated from the difference in film thickness before and after printing. The results are shown in Table 6.

  From the results in Table 6, it can be seen that the wear amount in the printing durability test of the photoreceptors (A5, J5A) is small and the printing durability is good.

Moreover, six types of polyester resins (resin Z to resin ZE) were manufactured by the following manufacturing method.
Production Example 31 (Resin Z)
Sodium hydroxide (7.20 g) and H ₂ O (282 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-1 (17.40 g) was added, stirred and dissolved therein, and the aqueous alkaline solution was transferred to a 1 L reaction vessel. Benzyltriethylammonium chloride (0.1798 g) and 2,3,5-trimethylphenol (0.3421 g) were then added sequentially to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (10.21 g), terephthalic acid chloride (4.22 g), isophthalic acid chloride (2.81 g) and dichloromethane (141 mL) was transferred into the dropping funnel. .
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (235 mL) was added and stirring was continued for 8 hours. Then, after adding acetic acid (2.61 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (283 mL), then twice with 0.1N hydrochloric acid (283 mL), and further washed with H ₂ O (283 mL). It went twice.
The organic layer after washing was poured into methanol (1880 mL), and the resulting precipitate was taken out by filtration and dried to obtain the desired resin Z. The obtained resin Z had a viscosity average molecular weight of 47,100. The repeating structure of the resin Z is shown below.

Production Example 32 (Resin ZA)
Sodium hydroxide (7.01 g) and H ₂ O (282 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-m (17.74 g) was added, stirred and dissolved therein, and then this aqueous alkaline solution was transferred to a 1 L reaction vessel. Benzyltriethylammonium chloride (0.1751 g) and 2,3,5-trimethylphenol (0.3330 g) were then sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (9.94 g), terephthalic acid chloride (4.10 g), isophthalic acid chloride (2.74 g) and dichloromethane (141 mL) was transferred into the dropping funnel. .
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (235 mL) was added and stirring was continued for 8 hours. Then, after adding acetic acid (2.54 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was isolate | separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (283 mL), then twice with 0.1N hydrochloric acid (283 mL), and further washed with H ₂ O (283 mL). We went twice.
The washed organic layer was poured into methanol (1880 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin ZA. The obtained resin ZA had a viscosity average molecular weight of 36,200. The repeating structure of the resin ZA is shown below.

Production Example 33 (Resin ZB)
Sodium hydroxide (10.80 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-I (26.10 g) was added, stirred and dissolved therein, and then this alkaline aqueous solution was transferred to a 1 L reaction vessel. Benzyltriethylammonium chloride (0.2698 g) and 2,3,5-trimethylphenol (0.5131 g) were then sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (15.32 g), terephthalic acid chloride (10.54 g) and dichloromethane (211 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 8 hours. Then, after adding acetic acid (3.92 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then twice with 0.1N hydrochloric acid (424 mL), and further washed with H ₂ O (424 mL). It went twice.
The washed organic layer was poured into methanol (2820 mL), and the resulting precipitate was filtered out and dried to obtain the desired resin ZB. The obtained resin ZB had a viscosity average molecular weight of 41,200. The repeating structure of the resin ZB is shown below.

Production Example 34 (Resin ZC)
Sodium hydroxide (10.80 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-I (26.10 g) was added, stirred and dissolved therein, and then this alkaline aqueous solution was transferred to a 1 L reaction vessel. Benzyltriethylammonium chloride (0.2698 g) and 2,3,5-trimethylphenol (0.5131 g) were then sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (15.32 g), isophthalic acid chloride (10.54 g) and dichloromethane (211 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 8 hours. Then, after adding acetic acid (3.92 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then twice with 0.1N hydrochloric acid (424 mL), and further washed with H ₂ O (424 mL). It went twice.
The washed organic layer was poured into methanol (2820 mL), and the resulting precipitate was filtered off and dried to obtain the desired resin ZC. The obtained resin ZC had a viscosity average molecular weight of 40,600. The repeating structure of the resin ZC is shown below.

Production Example 35 (Resin ZD)
Sodium hydroxide (10.50 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-m (26.57 g) was added, stirred and dissolved therein, and then this alkaline aqueous solution was transferred to a 1 L reaction vessel. Benzyltriethylammonium chloride (0.2623 g) and p- (tert-butyl) phenol (0.5503 g) were then sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (14.90 g), terephthalic acid chloride (10.25 g) and dichloromethane (211 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. As the polymerization progressed, insoluble components appeared in the organic layer, and removal and purification of the resin ZD were impossible. The repeating structure of the resin ZD is shown below.

Production Example 36 (Resin ZE)
Sodium hydroxide (10.50 g) and H ₂ O (423 mL) were weighed into a 500 mL beaker and dissolved with stirring. BP-m (26.57 g) was added, stirred and dissolved therein, and then this alkaline aqueous solution was transferred to a 1 L reaction vessel. Benzyltriethylammonium chloride (0.2623 g) and p- (tert-butyl) phenol (0.5503 g) were then sequentially added to the reaction vessel.
Separately, a mixed solution of diphenyl ether-4,4′-dicarboxylic acid chloride (14.90 g), isophthalic acid chloride (10.25 g) and dichloromethane (211 mL) was transferred into the dropping funnel.
While maintaining the external temperature of the polymerization tank at 20 ° C. and stirring the alkaline aqueous solution in the reaction tank, the dichloromethane solution was dropped from the dropping funnel over 1 hour. After further stirring for 4 hours, dichloromethane (352 mL) was added and stirring was continued for 8 hours. Then, after adding acetic acid (3.81 mL) and stirring for 30 minutes, stirring was stopped and the organic layer was separated. This organic layer was washed twice with 0.1N aqueous sodium hydroxide (424 mL), then twice with 0.1N hydrochloric acid (424 mL), and further washed with H ₂ O (424 mL). We went twice.
The washed organic layer was poured into methanol (2820 mL), and the resulting precipitate was removed by filtration and dried to obtain the desired resin ZE. The resulting resin ZE had a viscosity average molecular weight of 41,100. The repeating structure of the resin ZE is shown below.

Examples 26 and 27, Comparative Examples 20 to 25
A photoreceptor sheet was prepared using resins JA, JB, Z, ZA, ZB, ZC, ZD, and ZE, and an electrical property test and an abrasion test were performed. The results are shown in Table 7.

  From the results in Table 7, it can be seen that the amount of wear in the electrical property test and the wear test of the photoreceptor sheet (JA1, JB1) is small and good.

  In addition, this application is based on the Japanese application (Japanese Patent Application No. 2004-210571) for which it applied on July 16, 2004, The whole is used by reference.

It is a figure explaining an image forming apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Electrophotographic photoreceptor, 2 ... Charging device (charging roller), 3 ... Exposure device, 4 ... Developing device, 5 ... Transfer device, 6 ... Cleaning device, 7 ... Fixing device, 41 ... Developing tank, 42 ... Agitator, DESCRIPTION OF SYMBOLS 43 ... Supply roller, 44 ... Developing roller, 45 ... Restriction member, 71 ... Upper fixing member (fixing roller), 72 ... Lower fixing member (fixing roller), 73 ... Heating device

Claims (18)

A conductive substrate;
A photosensitive layer provided on the conductive substrate,
The electrophotographic photoreceptor, wherein the photosensitive layer contains a polyester resin having at least one repeating structure represented by the following general formulas (1) to (5).

(In general formula (5), {a / (a + b)}> 0.7.)
(In the general formula (1) to general formula (5), A is a compound having a structure represented by the following formula (A).)

(In formula (A), Ra ¹ and Ra ² are each independently a monovalent substituent that may have a hydrogen atom or a substituent, and n and m are each independently an integer of 0 to 4. .)
(In formula (1), B is a compound having a structure shown in the following formula (B).)

(In formula (B), R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, an aryl group, a halogen group, or an alkoxy group.)
(In formula (2), C is a compound having a structure shown in the following formula (C).)

(In the formula (C), R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group, an aryl group, a halogen group, or an alkoxy group.)
(In formula (3), D is a compound having a structure shown in the following formula (D).)

(In the formula (D), X ¹ represents a single bond or a divalent group.)
(In formula (4), E is a compound having a structure shown in the following formula (E)).

(In the formula (E), R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group, an aryl group, a halogen group, or an alkoxy group.)
(In formula (5), F is a compound having a structure shown in the following formula (F).)

(In the formula (F), X ² represents a single bond or a divalent group, and R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group, an aryl group, a halogen group, or an alkoxy group. K and l Each independently represents an integer of 1 to 4.)
(In formula (5), G is a compound having a structure represented by the following formula (G).)

(In the formula (G), X ³ represents a divalent group.)   2. The electrophotographic photoreceptor according to claim 1, wherein A in the general formulas (1) to (5) is derived from diphenyl ether dicarboxylic acid.   A in the general formula (1) to the general formula (5) is derived from diphenyl ether-2,2′-dicarboxylic acid, diphenyl ether-2,4′-dicarboxylic acid or diphenyl ether-4,4′-dicarboxylic acid. The electrophotographic photosensitive member according to claim 1, wherein   2. The electrophotographic photosensitive member according to claim 1, wherein A in the general formulas (1) to (5) is derived from diphenyl ether-4,4'-dicarboxylic acid.   B in the general formula (1) is bis (4-hydroxyphenyl) methane, (2-hydroxyphenyl) (4-hydroxyphenyl) methane, bis (2-hydroxyphenyl) methane, bis (4-hydroxy-3) 2. The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member is derived from -methylphenyl) methane or bis (4-hydroxy-3-ethylphenyl) methane.   2. The electrophotographic photosensitive member according to claim 1, wherein B in the general formula (1) is derived from bis (4-hydroxy-3-methylphenyl) methane.   C in the general formula (2) is 1,1-bis (4-hydroxyphenyl) ethane, 1- (2-hydroxyphenyl) -1- (4-hydroxyphenyl) ethane, 1,1-bis (2 Derived from -hydroxyphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane or 1,1-bis (4-hydroxy-3-ethylphenyl) ethane 1. The electrophotographic photosensitive member according to 1.   2. The electrophotographic photosensitive member according to claim 1, wherein C in the general formula (2) is derived from 1,1-bis (4-hydroxy-3-methylphenyl) ethane.   D in the general formula (3) is bis (4-hydroxy-3,5-dimethylphenyl) methane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane or 1,1-bis. 2. The electrophotographic photosensitive member according to claim 1, which is derived from (4-hydroxy-3,5-dimethylphenyl) cyclohexane.   E in the general formula (4) is bis (4-hydroxyphenyl) ether, (2-hydroxyphenyl) (4-hydroxyphenyl) ether, bis (2-hydroxyphenyl) ether, bis (4-hydroxy-3) 2. The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor is derived from -methylphenyl) ether or bis (4-hydroxy-3-ethylphenyl) ether.   2. The electrophotographic photoreceptor according to claim 1, wherein E in the general formula (4) is derived from bis (4-hydroxyphenyl) ether.   2. The electrophotographic photosensitive member according to claim 1, wherein G in the general formula (5) is derived from an aromatic dicarboxylic acid.   2. The electrophotographic photosensitive member according to claim 1, wherein G in the general formula (5) is derived from isophthalic acid or terephthalic acid.   The electrophotographic photoreceptor according to claim 1, wherein the polyester resin has a repeating structure represented by the general formula (2). The electrophotographic photoreceptor according to claim 1, wherein the photosensitive layer further contains a compound represented by the following general formula (6).

(In General Formula (6), Ar ^{1 to} Ar ⁶ each independently represent an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. M ¹ , m ² each independently represents 0 or 1. Q represents a direct bond or a divalent residue, and R ^{9 to} R ¹⁶ each independently represent a hydrogen atom or an alkyl which may have a substituent. A group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, n ^{1 to} n ⁴ each independently represents an integer of 0 to ^4. Ar ¹ ˜Ar ⁶ may be bonded to each other to form a cyclic structure.)   The electrophotographic photosensitive member according to claim 1, wherein the polyester resin has a viscosity average molecular weight (Mv) of 10,000 to 300,000. A photosensitive cartridge mounted on an image forming apparatus,
An electrophotographic photoreceptor according to claim 1,
A charging device for charging the electrophotographic photosensitive member to a predetermined potential;
At least one device selected from a developing device for supplying toner to the surface of the electrophotographic photosensitive member and a cleaning device for scraping and collecting residual toner attached to the surface of the electrophotographic photosensitive member;
A photoreceptor cartridge comprising: The electrophotographic photosensitive member according to claim 1,
A charging device for charging the electrophotographic photosensitive member;
An exposure device for forming an electrostatic latent image on the photosensitive surface of the electrophotographic photoreceptor;
A developing device for supplying toner to the surface of the electrophotographic photosensitive member;
A transfer device for transferring a toner image formed on the electrophotographic photoreceptor to a recording paper;
An image forming apparatus comprising: a fixing device that fixes the toner image transferred to the recording paper.

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